Barrier metal film production apparatus, barrier metal film production method, metal film production method, and metal film production apparatus

ABSTRACT

A Cl 2  gas plasma is generated at a site within a chamber between a substrate and a metal member. The metal member is etched with the Cl 2  gas plasma to form a precursor. A nitrogen gas is excited in a manner isolated from the chamber accommodating the substrate. A metal nitride is formed upon reaction between excited nitrogen and the precursor, and formed as a film on the substrate. After film formation of the metal nitride, a metal component of the precursor is formed as a film on the metal nitride on the substrate. In this manner, a barrier metal film with excellent burial properties and a very small thickness is produced at a high speed, with diffusion of metal being suppressed and adhesion to the metal being improved.

This application is a Divisional of co-pending application Ser. No.11/638,510, filed Dec. 14, 2006, which is a Divisional Application ofU.S. application Ser. No. 10/277,733, filed Oct. 23, 2002, which is nowabandoned, and for which priority is claimed under 35 U.S.C. §120; andthis application claims priority of Japanese Patent Application Nos.2001-348325, 2002-27738, 2002-44289, and 2002-44296, filed on Nov. 14,2001, Feb. 5, 2002, Feb. 21, 2002, and Feb. 21, 2002 under 35 U.S.C.§119. The contents of all of the aforementioned applications are herebyincorporated by reference herein in their entireties.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a production apparatus and a production methodfor a barrier metal film to be formed on the surface of a substrate foreliminating the diffusion of a metal into the substrate and retainingthe adhesion of the metal, when a metal film is formed on the surface ofthe substrate.

The present invention also relates to a metal film production method anda metal film production apparatus which can form a film of a metal, withthe diffusion of the metal being eliminated and the adhesion of themetal being retained, by treating the surface of a barrier metal filmproduced on a substrate.

2. Description of Related Art

Semiconductors with electrical wiring have increasingly used copper as amaterial for the wiring in order to increase the speed of switching,decrease transmission loss, and achieve a high density. In applying thecopper wiring, it has been common practice to perform the vapor phasegrowth method or plating on a substrate having a depression for wiringon its surface, thereby forming a copper film on the surface includingthe depression.

In forming the copper film on the surface of the substrate, a barriermetal film (for example, a nitride of tantalum, tungsten, titanium orsilicon) is prepared beforehand on the surface of the substrate in orderto eliminate the diffusion of copper into the substrate, and retain theadhesion of copper. When plating is employed, a copper shielding layeris formed on the barrier metal film by physical or chemical vapordeposition, and used also as an electrode. The barrier metal film hasbeen formed by physical vapor deposition such as sputtering.

The depression for wiring, formed on the surface of the substrate, tendsto be decreased in size, and a demand is expressed for a furtherreduction in the thickness of the barrier metal film. However, thebarrier metal film has been produced by use of sputtering, and itsdirectionality is not uniform. With a tiny depression on the surface ofthe substrate, therefore, the film is formed at the entrance of thedepression before being formed in the interior of the depression,resulting in insufficient burial of the depression. Also, the substratehas been badly damaged.

Additionally, the barrier metal film is prepared for the purposes ofpreventing the diffusion of copper into the substrate and retaining theadhesion of copper. Hence, a nitride of tantalum, tungsten or titaniumis formed as a first layer for prevention of copper diffusion, and anactive metal, such as tantalum, tungsten or titanium, is formed as asecond layer for retention of adhesion to copper. However, the barriermetal film is so thin that it poses difficulty at the present time inperforming both functions, the prevention of copper diffusion into thesubstrate and the retention of copper adhesion. A demand is growing forthe advent of a barrier metal film which accomplishes these twofunctions.

In particular, the wiring depression formed on the surface of thesubstrate is showing a tendency toward compactness, and further thinningof the barrier metal film is demanded. However, the necessary minimumfilm thickness has increased, if the barrier metal film is constructedin a two-layer structure by forming a nitride of tantalum, tungsten ortitanium as a first layer for prevention of copper diffusion, andforming an active metal, such as tantalum, tungsten or titanium, as asecond layer for retention of adhesion to copper.

SUMMARY OF THE INVENTION

The present invention has been accomplished in light of thecircumstances described above. An object of the invention is to providea barrier metal film production apparatus and a barrier metal filmproduction method which can form a barrier metal film with excellentburial properties and a very small thickness at a high speed. Anotherobject of the invention is to provide a barrier metal film productionapparatus and a barrier metal film production method which can form abarrier metal film with excellent adhesion to a metal formed as a filmon the surface of the substrate. Still another object of the inventionis to provide a metal film production method and a metal film productionapparatus capable of forming a barrier metal film which, although verythin, prevents diffusion of a metal and retains adhesion to the metal.

According to the present invention, there is provided a barrier metalfilm production apparatus, comprising:

a chamber accommodating a substrate;

a metallic etched member provided in the chamber at a position opposedto the substrate;

source gas supply means for supplying a source gas containing a halogento an interior of the chamber between the substrate and the etchedmember;

plasma generation means which converts an atmosphere within the chamberinto a plasma to generate a source gas plasma so that the etched memberis etched with the source gas plasma to form a precursor from a metalcomponent contained in the etched member and the source gas;

excitation means for exciting a nitrogen-containing gas in a mannerisolated from the chamber;

formation means for forming a metal nitride upon reaction betweennitrogen excited by the excitation means and the precursor; and

control means which makes a temperature of the substrate lower than atemperature of the formation means to form the metal nitride as a filmon the substrate.

Thus, a barrier metal film comprising a film of a metal nitride andsuppressing diffusion can be prepared by forming a metal with the use ofa plasma. The barrier metal film can be formed uniformly to a smallthickness. Consequently, the barrier metal film can be formed highlyaccurately at a high speed with excellent burial properties in a verysmall thickness even to the interior of a tiny depression, for exampleseveral hundred nanometers wide, which has been provided in thesubstrate.

According to the present invention, there is also provided a barriermetal film production apparatus, comprising:

a chamber accommodating a substrate;

a metallic etched member provided in the chamber at a position opposedto the substrate;

source gas supply means for supplying a source gas containing a halogento an interior of the chamber between the substrate and the etchedmember;

plasma generation means which converts an atmosphere within the chamberinto a plasma to generate a source gas plasma so that the etched memberis etched with the source gas plasma to form a precursor from a metalcomponent contained in the etched member and the source gas;

excitation means for exciting a nitrogen-containing gas in a mannerisolated from the chamber;

formation means for forming a metal nitride upon reaction betweennitrogen excited by the excitation means and the precursor; and

control means which makes a temperature of the substrate lower than atemperature of the formation means to form the metal nitride as a filmon the substrate, and after film formation of the metal nitride, stopssupply of the nitrogen-containing gas, and makes the temperature of thesubstrate lower than a temperature of the etched member to form themetal component of the precursor as a film on the metal nitride on thesubstrate.

Thus, a barrier metal film comprising a film of a metal nitride and ametal film and with diffusion suppressed and adhesion improved can beprepared by forming a metal by plasmas. The barrier metal film can beformed uniformly to a small thickness. Consequently, the barrier metalfilm can be formed highly accurately at a high speed with excellentburial properties in a very small thickness even to the interior of atiny depression, for example several hundred nanometers wide, which hasbeen provided in the substrate.

According to the present invention, there is also provided a barriermetal film production apparatus, comprising:

a chamber accommodating a substrate;

a metallic etched member provided in the chamber at a position opposedto the substrate;

source gas supply means for supplying a source gas containing a halogento an interior of the chamber between the substrate and the etchedmember;

nitrogen-containing gas supply means for supplying a nitrogen-containinggas to an interior of the chamber between the substrate and the etchedmember;

plasma generation means which converts an atmosphere within the chamberinto a plasma to generate a source gas plasma and a nitrogen-containinggas plasma so that the etched member is etched with the source gasplasma to form a precursor from a metal component contained in theetched member and the source gas, and that a metal nitride is formedupon reaction between nitrogen and the precursor; and

control means which makes a temperature of the substrate lower than atemperature of the etched member to form the metal nitride as a film onthe substrate.

Thus, a barrier metal film comprising a film of a metal nitride and ametal film and with diffusion suppressed can be prepared by forming ametal by plasmas. The barrier metal film can be formed uniformly to asmall thickness. Also, the supply lines for gases can be simplified, andthe number of plasma sources can be decreased, so that the product costcan be reduced. Consequently, the barrier metal film can be formedhighly accurately at a high speed and at a low cost with excellentburial properties in a very small thickness even to the interior of atiny depression, for example several hundred nanometers wide, which hasbeen provided in the substrate.

According to the present invention, there is also provided a barriermetal film production apparatus, comprising:

a chamber accommodating a substrate;

a metallic etched member provided in the chamber at a position opposedto the substrate;

source gas supply means for supplying a source gas containing a halogento an interior of the chamber between the substrate and the etchedmember;

nitrogen-containing gas supply means for supplying a nitrogen-containinggas to an interior of the chamber between the substrate and the etchedmember;

plasma generation means which converts an atmosphere within the chamberinto a plasma to generate a source gas plasma and a nitrogen-containinggas plasma so that the etched member is etched with the source gasplasma to form a precursor from a metal component contained in theetched member and the source gas, and that a metal nitride is formedupon reaction between nitrogen and the precursor; and

control means which makes a temperature of the substrate lower than atemperature of the etched member to form the metal nitride as a film onthe substrate, then stops supply of the nitrogen-containing gas, andmakes the temperature of the substrate lower than the temperature of theetched member to form the metal component of the precursor as a film onthe metal nitride on the substrate.

Thus, a barrier metal film comprising a film of a metal nitride and ametal film and with diffusion suppressed and adhesion improved can beprepared by forming a metal by plasmas. The barrier metal film can beformed uniformly to a small thickness. Also, the supply lines for gasescan be simplified, and the number of plasma sources can be decreased, sothat the product cost can be reduced. Consequently, the barrier metalfilm can be formed highly accurately at a high speed and at a low costwith excellent burial properties in a very small thickness even to theinterior of a tiny depression, for example several hundred nanometerswide, which has been provided in the substrate.

According to the present invention, there is also provided a barriermetal film production method comprising:

supplying a source gas containing a halogen to an interior of a chamberbetween a substrate and a metallic etched member;

converting an atmosphere within the chamber into a plasma to generate asource gas plasma so that the etched member is etched with the sourcegas plasma to form a precursor from a metal component contained in theetched member and the source gas;

exciting a nitrogen-containing gas in a manner isolated from the chamberaccommodating the substrate;

forming a metal nitride upon reaction between excited nitrogen and theprecursor; and

making a temperature of the substrate lower than a temperature of meansfor formation of the metal nitride to form the metal nitride as a filmon the substrate.

Thus, a barrier metal film comprising a film of a metal nitride andsuppressing diffusion can be prepared by forming a metal by plasma. Thebarrier metal film can be formed uniformly to a small thickness.Consequently, the barrier metal film can be formed highly accurately ata high speed with excellent burial properties in a very small thicknesseven to the interior of a tiny depression, for example several hundrednanometers wide, which has been provided in the substrate.

According to the present invention, there is also provided a barriermetal film production method comprising:

supplying a source gas containing a halogen to an interior of a chamberbetween a substrate and a metallic etched member;

converting an atmosphere within the chamber into a plasma to generate asource gas plasma so that the etched member is etched with the sourcegas plasma to form a precursor from a metal component contained in theetched member and the source gas;

exciting a nitrogen-containing gas in a manner isolated from the chamberaccommodating the substrate;

forming a metal nitride upon reaction between excited nitrogen and theprecursor;

making a temperature of the substrate lower than a temperature of meansfor formation of the metal nitride to form the metal nitride as a filmon the substrate; and

after film formation of the metal nitride, stopping supply of thenitrogen-containing gas, and making the temperature of the substratelower than a temperature of the etched member to form the metalcomponent of the precursor as a film on the metal nitride on thesubstrate.

Thus, a barrier metal film comprising a film of a metal nitride and ametal film and with diffusion suppressed and adhesion improved can beprepared by forming a metal by plasmas. The barrier metal film can beformed uniformly to a small thickness. Consequently, the barrier metalfilm can be formed highly accurately at a high speed with excellentburial properties in a very small thickness even to the interior of atiny depression, for example several hundred nanometers wide, which hasbeen provided in the substrate.

According to the present invention, there is also provided a barriermetal film production method comprising:

supplying a source gas containing a halogen and a nitrogen-containinggas to an interior of a chamber between a substrate and a metallicetched member;

converting an atmosphere within the chamber into a plasma to generate asource gas plasma and a nitrogen-containing gas plasma so that theetched member is etched with the source gas plasma to form a precursorfrom a metal component contained in the etched member and the sourcegas, and that a metal nitride is formed upon reaction between nitrogenand the precursor; and

making a temperature of the substrate lower than a temperature of theetched member to form the metal nitride as a film on the substrate.

Thus, a barrier metal film comprising a film of a metal nitride and withdiffusion suppressed can be prepared by forming a metal by plasmas. Thebarrier metal film can be formed uniformly to a small thickness. Also,the supply line for gases can be simplified, and the number of plasmasources can be decreased, so that the product cost can be reduced.Consequently, the barrier metal film can be formed highly accurately ata high speed and at a low cost with excellent burial properties in avery small thickness even to the interior of a tiny depression, forexample several hundred nanometers wide, which has been provided in thesubstrate.

According to the present invention, there is also provided a barriermetal film production method comprising:

supplying a source gas containing a halogen and a nitrogen-containinggas to an interior of a chamber between a substrate and a metallicetched member;

converting an atmosphere within the chamber into a plasma to generate asource gas plasma and a nitrogen-containing gas plasma so that theetched member is etched with the source gas plasma to form a precursorfrom a metal component contained in the etched member and the sourcegas, and that a metal nitride is formed upon reaction between nitrogenand the precursor;

making a temperature of the substrate lower than a temperature of theetched member to form the metal nitride as a film on the substrate; and

after film formation of the metal nitride, stopping supply of thenitrogen-containing gas, and making the temperature of the substratelower than the temperature of the etched member to form the metalcomponent of the precursor as a film on the metal nitride on thesubstrate.

Thus, a barrier metal film comprising a film of a metal nitride and ametal film and with diffusion suppressed and adhesion improved can beprepared by forming a metal by plasmas. The barrier metal film can beformed uniformly to a small thickness. Also, the supply line for gasescan be simplified, and the number of plasma sources can be decreased, sothat the product cost can be reduced. Consequently, the barrier metalfilm can be formed highly accurately at a high speed and at a low costwith excellent burial properties in a very small thickness even to theinterior of a tiny depression, for example several hundred nanometerswide, which has been provided in the substrate.

According to the present invention, there is also provided a barriermetal film production apparatus, comprising:

a chamber accommodating a substrate;

a metallic etched member provided in the chamber at a position opposedto the substrate;

source gas supply means for supplying a source gas containing a halogeninto the chamber;

nitrogen-containing gas supply means for supplying a gas containingnitrogen into the chamber;

plasma generation means which converts an atmosphere within the chamberinto a plasma to generate a source gas plasma so that the etched memberis etched with the source gas plasma to form a precursor from a metalcomponent contained in the etched member and the source gas, and whichconverts the atmosphere within the chamber into a plasma to generate anitrogen-containing gas plasma so that a metal nitride is formed uponreaction between nitrogen and the precursor;

control means which makes a temperature of the substrate lower than atemperature of the plasma generation means to form the metal nitride asa barrier metal film on a surface of the substrate;

diluent gas supply means for supplying a diluent gas to a site above thesurface of the substrate; and

surface treatment plasma generation means for performing a surfacetreatment which converts the atmosphere within the chamber into a plasmato generate a diluent gas plasma so that nitrogen atoms in a superficiallayer of the barrier metal film are removed by the diluent gas plasma todecrease a nitrogen content of the superficial layer relative to aninterior of a matrix of the barrier metal film.

Thus, a barrier metal film comprising a metal nitride layer and a metallayer can be prepared without the increase of the film thickness.Consequently, a barrier metal film production apparatus can be achievedwhich is capable of forming a barrier metal film at a high speed withexcellent burial properties in a very small thickness, and also forminga barrier metal film with excellent adhesion to a metal formed as a filmon the surface of the barrier metal film.

The barrier metal film production apparatus may further comprise oxygengas supply means for supplying an oxygen gas into the chamberimmediately before formation of the most superficial layer of thebarrier metal film is completed; and oxygen plasma generation meanswhich converts the atmosphere within the chamber into a plasma togenerate an oxygen gas plasma so that an oxide layer is formed on themost superficial layer of the barrier metal film.

Thus, because of an oxide layer, if a metal is deposited on the surfaceof the barrier metal film, wettability by the metal can be renderedsatisfactory, thus increasing adhesion.

According to the present invention, there is also provided a barriermetal film production apparatus, comprising:

a chamber accommodating a substrate;

a metallic etched member provided in the chamber at a position opposedto the substrate;

source gas supply means for supplying a source gas containing a halogeninto the chamber;

nitrogen-containing gas supply means for supplying a gas containingnitrogen into the chamber;

plasma generation means which converts an atmosphere within the chamberinto a plasma to generate a source gas plasma so that the etched memberis etched with the source gas plasma to form a precursor from a metalcomponent contained in the etched member and the source gas, and whichconverts the atmosphere within the chamber into a plasma to generate anitrogen-containing gas plasma so that a metal nitride is formed uponreaction between nitrogen and the precursor;

control means which makes a temperature of the substrate lower than atemperature of the plasma generation means to form the metal nitride asa barrier metal film on a surface of the substrate;

oxygen gas supply means for supplying an oxygen gas to a site above thesurface of the substrate; and

oxygen plasma generation means for performing a surface treatment whichconverts the atmosphere within the chamber into a plasma to generate anoxygen gas plasma so that nitrogen atoms in a superficial layer of thebarrier metal film are removed by the oxygen gas plasma to decrease anitrogen content of the superficial layer relative to an interior of amatrix of the barrier metal film, and at the same time, forming an oxidelayer on the most superficial layer of the barrier metal film.

Thus, a barrier metal film comprising a metal nitride layer and a metallayer can be prepared with a minimum nozzle construction without theincrease of the film thickness, and an oxide layer gives satisfactorywettability by a metal deposited on the surface of the barrier metalfilm. Consequently, a barrier metal film production apparatus can beachieved which is capable of forming a barrier metal film at a highspeed with excellent burial properties in a very small thickness, andalso forming a barrier metal film with excellent adhesion to a metalformed as a film on the surface of the barrier metal film.

According to the present invention, there is also provided a barriermetal film production apparatus, comprising:

a chamber accommodating a substrate;

a metallic etched member provided in the chamber at a position opposedto the substrate;

source gas supply means for supplying a source gas containing a halogeninto the chamber;

nitrogen-containing gas supply means for supplying a gas containingnitrogen into the chamber;

plasma generation means which converts an atmosphere within the chamberinto a plasma to generate a source gas plasma so that the etched memberis etched with the source gas plasma to form a precursor from a metalcomponent contained in the etched member and the source gas, and whichconverts the atmosphere within the chamber into a plasma to generate anitrogen-containing gas plasma so that a metal nitride is formed uponreaction between nitrogen and the precursor;

control means which makes a temperature of the substrate lower than atemperature of the plasma generation means to form the metal nitride asa film, for use as a barrier metal film, on a surface of the substrate;

oxygen gas supply means for supplying an oxygen gas into the chamberimmediately before formation of the most superficial layer of thebarrier metal film is completed; and

oxygen plasma generation means which converts the atmosphere within thechamber into a plasma to generate an oxygen gas plasma so that an oxidelayer is formed on the most superficial layer of the barrier metal film.

Thus, a barrier metal film comprising a metal nitride layer can beprepared without the increase of the film thickness, and an oxide layergives satisfactory wettability by a metal deposited on the surface ofthe barrier metal film. Consequently, a barrier metal film productionapparatus can be achieved which is capable of forming a barrier metalfilm at a high speed with excellent burial properties in a very smallthickness, and also forming a barrier metal film with excellent adhesionto a metal formed as a film on the surface of the barrier metal film.

According to the present invention, there is also provided a barriermetal film production apparatus, comprising:

a chamber accommodating a substrate;

a metallic etched member provided in the chamber at a position opposedto the substrate;

source gas supply means for supplying a source gas containing a halogeninto the chamber;

nitrogen-containing gas supply means for supplying a gas containingnitrogen into the chamber;

plasma generation means which converts an atmosphere within the chamberinto a plasma to generate a source gas plasma so that the etched memberis etched with the source gas plasma to form a precursor from a metalcomponent contained in the etched member and the source gas, and whichconverts the atmosphere within the chamber into a plasma to generate anitrogen-containing gas plasma so that a metal nitride is formed uponreaction between nitrogen and the precursor;

control means which makes a temperature of the substrate lower than atemperature of the plasma generation means to form the metal nitride asa film on a surface of the substrate, then makes the temperature of thesubstrate lower than the temperature of the plasma generation means andstops supply of the gas containing nitrogen from the nitrogen-containinggas supply means, thereby forming the metal component of the precursoras a film on the metal nitride for use as a barrier metal film;

oxygen gas supply means for supplying an oxygen gas into the chamberimmediately before formation of the most superficial layer of thebarrier metal film is completed; and

oxygen plasma generation means which converts the atmosphere within thechamber into a plasma to generate an oxygen gas plasma so that an oxidelayer is formed on the most superficial layer of the barrier metal film.

Thus, a barrier metal film comprising a metal nitride layer and a metallayer can be prepared without the increase of the film thickness, and anoxide layer gives satisfactory wettability by a metal deposited on thesurface of the barrier metal film. Consequently, a barrier metal filmproduction apparatus can be achieved which is capable of forming abarrier metal film at a high speed with excellent burial properties, andalso forming a barrier metal film with excellent adhesion to a metalformed as a film on the surface of the barrier metal film.

According to the present invention, there is also provided a barriermetal film production apparatus, comprising:

a chamber accommodating a substrate;

a metallic etched member provided in the chamber at a position opposedto the substrate;

source gas supply means for supplying a source gas containing a halogeninto the chamber;

plasma generation means which converts an atmosphere within the chamberinto a plasma to generate a source gas plasma so that the etched memberis etched with the source gas plasma to form a precursor from a metalcomponent contained in the etched member and the source gas;

excitation means for exciting a gas containing nitrogen in a mannerisolated from the chamber;

formation means for forming a metal nitride upon reaction betweennitrogen excited by the excitation means and the precursor;

control means which makes a temperature of the substrate lower than atemperature of the formation means to form the metal nitride as a filmon the substrate for use as a barrier metal film;

oxygen gas supply means for supplying an oxygen gas into the chamberimmediately before formation of the most superficial layer of thebarrier metal film is completed; and

oxygen plasma generation means which converts the atmosphere within thechamber into a plasma to generate an oxygen gas plasma so that an oxidelayer is formed on the most superficial layer of the barrier metal film.

Thus, a barrier metal film comprising a metal nitride layer can beprepared without the increase of the film thickness, an oxide layergives satisfactory wettability by a metal deposited on the surface ofthe barrier metal film, and the substrate can be free from exposure to anitrogen-containing gas plasma. Consequently, a barrier metal filmproduction apparatus can be achieved which is capable of forming abarrier metal film at a high speed with excellent burial properties in avery small thickness without exerting the influence of thenitrogen-containing gas plasma upon the substrate, and also forming abarrier metal film with excellent adhesion to a metal formed as a filmon the surface of the barrier metal film.

According to the present invention, there is also provided a barriermetal film production apparatus, comprising:

a chamber accommodating a substrate;

a metallic etched member provided in the chamber at a position opposedto the substrate;

source gas supply means for supplying a source gas containing a halogeninto the chamber;

plasma generation means which converts an atmosphere within the chamberinto a plasma to generate a source gas plasma so that the etched memberis etched with the source gas plasma to form a precursor from a metalcomponent contained in the etched member and the source gas;

excitation means for exciting a gas containing nitrogen in a mannerisolated from the chamber;

formation means for forming a metal nitride upon reaction betweennitrogen excited by the excitation means and the precursor;

control means which makes a temperature of the substrate lower than atemperature of the formation means to form the metal nitride as a filmon the substrate, and after film formation of the metal nitride, stopssupply of the nitrogen-containing gas and makes the temperature of thesubstrate lower than a temperature of the etched member, thereby formingthe metal component of the precursor as a film on the metal nitride onthe substrate for use as a barrier metal film;

oxygen gas supply means for supplying an oxygen gas into the chamberimmediately before formation of the most superficial layer of thebarrier metal film is completed; and

oxygen plasma generation means which converts the atmosphere within thechamber into a plasma to generate an oxygen gas plasma so that an oxidelayer is formed on the most superficial layer of the barrier metal film.

Thus, a barrier metal film comprising a metal nitride layer can beprepared without the increase of the film thickness, an oxide layergives satisfactory wettability by a metal deposited on the surface ofthe barrier metal film, and the substrate can be free from exposure to anitrogen-containing gas plasma. Consequently, a barrier metal filmproduction apparatus can be achieved which is capable of forming abarrier metal film at a high speed with excellent burial propertieswithout exerting the influence of the nitrogen-containing gas plasmaupon the substrate, and also forming a barrier metal film with excellentadhesion to a metal formed as a film on the surface of the barrier metalfilm.

The barrier metal film production apparatus may further comprisehydrogen gas supply means for supplying a hydrogen gas into the chamber;and hydroxyl group plasma generation means which converts the atmospherewithin the chamber into a plasma to generate a hydrogen gas plasma sothat hydroxyl groups are formed on the oxide layer.

Thus, hydroxyl groups are formed, so that hydrophilicity can beincreased, and adhesion of a metal deposited on the surface can befurther increased.

According to the present invention, there is also provided a barriermetal film production method comprising:

supplying a source gas containing a halogen and a nitrogen-containinggas to an interior of a chamber between a substrate and a metallicetched member;

converting an atmosphere within the chamber into a plasma to generate asource gas plasma so that the etched member is etched with the sourcegas plasma to form a precursor from a metal component contained in theetched member and the source gas, and also converting the atmospherewithin the chamber into a plasma to generate a nitrogen-containing gasplasma so that a metal nitride is formed upon reaction between nitrogenand the precursor;

making a temperature of the substrate lower than a temperature of plasmageneration means to form the metal nitride as a barrier metal film on asurface of the substrate;

supplying a diluent gas to a site within the chamber above the surfaceof the substrate; and

performing a surface treatment which converts the atmosphere within thechamber into a plasma to generate a diluent gas plasma so that nitrogenatoms in a superficial layer of the barrier metal film are removed bythe diluent gas plasma to decrease a nitrogen content of the superficiallayer relative to an interior of a matrix of the barrier metal film.

Thus, a barrier metal film comprising a metal nitride layer and a metallayer can be prepared without the increase of the film thickness.Consequently, a barrier metal film production method can be achievedwhich is capable of forming a barrier metal film at a high speed withexcellent burial properties in a very small thickness, and also forminga barrier metal film with excellent adhesion to a metal formed as a filmon the surface of the barrier metal film.

The barrier metal film production method may further comprise supplyingan oxygen gas into the chamber immediately before formation of the mostsuperficial layer of the barrier metal film is completed; and convertingthe atmosphere within the chamber into a plasma to generate an oxygengas plasma so that an oxide layer is formed on the most superficiallayer of the barrier metal film.

Thus, the oxide layer gives satisfactory wettability by a metaldeposited on the surface of the barrier metal film, thereby increasingadhesion to the metal.

According to the present invention, there is also provided a barriermetal film production method comprising:

supplying a source gas containing a halogen and a nitrogen-containinggas to an interior of a chamber between a substrate and a metallicetched member;

converting an atmosphere within the chamber into a plasma to generate asource gas plasma so that the etched member is etched with the sourcegas plasma to form a precursor from a metal component contained in theetched member and the source gas, and also converting the atmospherewithin the chamber into a plasma to generate a nitrogen-containing gasplasma so that a metal nitride is formed upon reaction between nitrogenand the precursor;

making a temperature of the substrate lower than a temperature of plasmageneration means to form the metal nitride as a barrier metal film on asurface of the substrate;

supplying an oxygen gas to a site above the surface of the substrate;and

performing a surface treatment which converts the atmosphere within thechamber into a plasma to generate an oxygen gas plasma so that nitrogenatoms in a superficial layer of the barrier metal film are removed bythe oxygen gas plasma to decrease a nitrogen content of the superficiallayer relative to an interior of a matrix of the barrier metal film,while forming an oxide layer on the most superficial layer of thebarrier metal film.

Thus, a barrier metal film comprising a metal nitride layer and a metallayer can be prepared with a minimum nozzle construction without theincrease of the film thickness, and an oxide layer gives satisfactorywettability by a metal deposited on the surface of the barrier metalfilm. Consequently, a barrier metal film production method can beachieved which is capable of forming a barrier metal film at a highspeed with excellent burial properties in a very small thickness, andalso forming a barrier metal film with excellent adhesion to a metalformed as a film on the surface of the barrier metal film.

According to the present invention, there is also provided a barriermetal film production method comprising:

supplying a source gas containing a halogen and a nitrogen-containinggas to an interior of a chamber between a substrate and a metallicetched member;

converting an atmosphere within the chamber into a plasma to generate asource gas plasma so that the etched member is etched with the sourcegas plasma to form a precursor from a metal component contained in theetched member and the source gas, and also converting the atmospherewithin the chamber into a plasma to generate a nitrogen-containing gasplasma so that a metal nitride is formed upon reaction between nitrogenand the precursor;

making a temperature of the substrate lower than a temperature of plasmageneration means to form the metal nitride as a film on a surface of thesubstrate for use as a barrier metal film;

supplying an oxygen gas into the chamber immediately before formation ofthe most superficial layer of the barrier metal film is completed; and

converting the atmosphere within the chamber into a plasma to generatean oxygen gas plasma so that an oxide layer is formed on the mostsuperficial layer of the barrier metal film.

Thus, a barrier metal film comprising a metal nitride layer can beprepared without the increase of the film thickness, and an oxide layergives satisfactory wettability by a metal deposited on the surface ofthe barrier metal film. Consequently, a barrier metal film productionmethod can be achieved which is capable of forming a barrier metal filmat a high speed with excellent burial properties in a very smallthickness, and also forming a barrier metal film with excellent adhesionto a metal formed as a film on the surface of the barrier metal film.

According to the present invention, there is also provided a barriermetal film production method comprising:

supplying a source gas containing a halogen and a nitrogen-containinggas to an interior of a chamber between a substrate and a metallicetched member;

converting an atmosphere within the chamber into a plasma to generate asource gas plasma so that the etched member is etched with the sourcegas plasma to form a precursor from a metal component contained in theetched member and the source gas, and also converting the atmospherewithin the chamber into a plasma to generate a nitrogen-containing gasplasma so that a metal nitride is formed upon reaction between nitrogenand the precursor;

making a temperature of the substrate lower than a temperature of plasmageneration means to form the metal nitride as a film on a surface of thesubstrate, then making the temperature of the substrate lower than thetemperature of the plasma generation means and stopping supply of thegas containing nitrogen, thereby forming the metal component of theprecursor as a film on the metal nitride for use as a barrier metalfilm;

supplying an oxygen gas into the chamber immediately before formation ofthe most superficial layer of the barrier metal film is completed; and

converting the atmosphere within the chamber into a plasma to generatean oxygen gas plasma so that an oxide layer is formed on the mostsuperficial layer of the barrier metal film.

Thus, a barrier metal film comprising a metal nitride layer and a metallayer can be prepared without the increase of the film thickness, and anoxide layer gives satisfactory wettability by a metal deposited on thesurface of the barrier metal film. Consequently, a barrier metal filmproduction method can be achieved which is capable of forming a barriermetal film at a high speed with excellent burial properties, and alsoforming a barrier metal film with excellent adhesion to a metal formedas a film on the surface of the barrier metal film.

According to the present invention, there is also provided a barriermetal film production method comprising:

supplying a source gas containing a halogen and a nitrogen-containinggas to an interior of a chamber between a substrate and a metallicetched member;

converting an atmosphere within the chamber into a plasma to generate asource gas plasma so that the etched member is etched with the sourcegas plasma to form a precursor from a metal component contained in theetched member and the source gas, and also exciting the gas containingnitrogen in a manner isolated from the chamber accommodating thesubstrate;

forming a metal nitride upon reaction between excited nitrogen and theprecursor;

making a temperature of the substrate lower than a temperature of meansfor formation of the metal nitride to form the metal nitride as a filmon the substrate for use as a barrier metal film;

supplying an oxygen gas at a site above a surface of the substrateimmediately before formation of the most superficial layer of thebarrier metal film is completed; and

converting the atmosphere within the chamber into a plasma to generatean oxygen gas plasma so that an oxide layer is formed on the mostsuperficial layer of the barrier metal film.

Thus, a barrier metal film comprising a metal nitride layer can beprepared without the increase of the film thickness, an oxide layergives satisfactory wettability by a metal deposited on the surface ofthe barrier metal film, and the substrate can be free from exposure to anitrogen-containing gas plasma. Consequently, a barrier metal filmproduction method can be achieved which is capable of forming a barriermetal film at a high speed with excellent burial properties in a verysmall thickness without exerting the influence of thenitrogen-containing gas plasma upon the substrate, and also forming abarrier metal film with excellent adhesion to a metal formed as a filmon the surface of the barrier metal film.

According to the present invention, there is also provided a barriermetal film production method comprising:

supplying a source gas containing a halogen and a nitrogen-containinggas to an interior of a chamber between a substrate and a metallicetched member;

converting an atmosphere within the chamber into a plasma to generate asource gas plasma so that the etched member is etched with the sourcegas plasma to form a precursor from a metal component contained in theetched member and the source gas, and also exciting the gas containingnitrogen in a manner isolated from the chamber accommodating thesubstrate;

forming a metal nitride upon reaction between excited nitrogen and theprecursor;

making a temperature of the substrate lower than a temperature of meansfor formation of the metal nitride to form the metal nitride as a filmon the substrate, and after film formation of the metal nitride,stopping supply of the nitrogen-containing gas and making thetemperature of the substrate lower than a temperature of the etchedmember, thereby forming the metal component of the precursor as a filmon the metal nitride on the substrate for use as a barrier metal film;

supplying an oxygen gas at a site above a surface of the substrateimmediately before formation of the most superficial layer of thebarrier metal film is completed; and

converting the atmosphere within the chamber into a plasma to generatean oxygen gas plasma so that an oxide layer is formed on the mostsuperficial layer of the barrier metal film.

Thus, a barrier metal film comprising a metal nitride layer can beprepared without the increase of the film thickness, an oxide layergives satisfactory wettability by a metal deposited on the surface ofthe barrier metal film, and the substrate can be free from exposure to anitrogen-containing gas plasma. Consequently, a barrier metal filmproduction method can be achieved which is capable of forming a barriermetal film at a high speed with excellent burial properties withoutexerting the influence of the nitrogen-containing gas plasma upon thesubstrate, and also forming a barrier metal film with excellent adhesionto a metal formed as a film on the surface of the barrier metal film.

The barrier metal film production method may further comprise supplyinga hydrogen gas into the chamber; and converting the atmosphere withinthe chamber into a plasma to generate a hydrogen gas plasma so thathydroxyl groups are formed on the oxide layer.

Thus, hydrophilicity can be increased, so that adhesion of a metaldeposited on the surface can be further increased.

According to the present invention, there is also provided a barriermetal film production method involving treatment of a surface of asubstrate having a barrier metal film of a metal nitride formed thereon,comprising:

performing a surface treatment which removes nitrogen atoms in asuperficial layer of the barrier metal film to decrease a nitrogencontent of the superficial layer relative to an interior of a matrix ofthe barrier metal film, thereby substantially forming a metal layer onthe superficial layer.

Thus, the substantial metal layer and the metal nitride layer can beformed with a single-layer thickness, and a barrier metal film with avery small thickness can be produced, with diffusion of metal beingprevented and adhesion to the metal being retained. Consequently, ametal wiring process can be stabilized.

According to the present invention, there is also provided a metal filmcomprising a metal layer substantially formed on a superficial layer ofa barrier metal film of a metal nitride formed on a surface of asubstrate, said metal layer being formed by performing a surfacetreatment which removes nitrogen atoms in the superficial layer of thebarrier metal film to decrease a nitrogen content of the superficiallayer relative to an interior of a matrix of the barrier metal film.

Thus, there is obtained a metal film which has a barrier metal filmcomprising the substantial metal layer and the metal nitride layerformed with a single-layer thickness, and produced with a very smallthickness, with diffusion of metal being prevented and adhesion to themetal being retained, and which can stabilize a metal wiring process.

According to the present invention, there is also provided a barriermetal film production method involving treatment of a surface of asubstrate having a barrier metal film of a metal nitride formed thereon,comprising:

performing a surface treatment which etches the barrier metal film onthe surface of the substrate with a diluent gas plasma to flatten thebarrier metal film.

Thus, a barrier metal film can be produced, with diffusion of metalbeing prevented and adhesion to the metal being retained. Consequently,a metal wiring process can be stabilized.

According to the present invention, there is also provided a barriermetal film production method involving treatment of a surface of asubstrate having a barrier metal film of a metal nitride formed thereon,comprising:

performing a surface treatment which etches the barrier metal film onthe surface of the substrate with a diluent gas plasma to flatten thebarrier metal film, and removes nitrogen atoms in a superficial layer ofthe barrier metal film by the diluent gas plasma to decrease a nitrogencontent of the superficial layer relative to an interior of a matrix ofthe barrier metal film.

Thus, the substantial metal layer and the metal nitride layer can beformed with a single-layer thickness, and a barrier metal film with avery small thickness can be produced, with diffusion of metal beingprevented and adhesion to the metal being retained. Consequently, ametal wiring process can be stabilized.

According to the present invention, there is also provided a metal filmproduction method comprising:

supplying a source gas containing a halogen to an interior of a chamberbetween a substrate and a metallic etched member;

converting an atmosphere within the chamber into a plasma to generate asource gas plasma so that the etched member is etched with the sourcegas plasma to form a precursor from a metal component contained in theetched member and the source gas, and also exciting a gas containingnitrogen in a manner isolated from the chamber accommodating thesubstrate;

forming a metal nitride upon reaction between excited nitrogen and theprecursor;

making a temperature of the substrate lower than a temperature of meansfor formation of the metal nitride to form the metal nitride as a filmon the substrate for use as a barrier metal film; and

performing a surface treatment which etches the barrier metal film on asurface of the substrate with a diluent gas plasma to flatten thebarrier metal film.

Thus, a barrier metal film can be produced such that the barrier metalfilm is prepared, and then subjected to a treatment for preventingdiffusion of metal and retaining adhesion to the metal. Consequently, ametal wiring process can be stabilized.

According to the present invention, there is also provided a metal filmproduction method comprising:

supplying a source gas containing a halogen to an interior of a chamberbetween a substrate and a metallic etched member;

converting an atmosphere within the chamber into a plasma to generate asource gas plasma so that the etched member is etched with the sourcegas plasma to form a precursor from a metal component contained in theetched member and the source gas, and also exciting a gas containingnitrogen in a manner isolated from the chamber accommodating thesubstrate;

forming a metal nitride upon reaction between excited nitrogen and theprecursor;

making a temperature of the substrate lower than a temperature of meansfor formation of the metal nitride to form the metal nitride as a filmon the substrate for use as a barrier metal film; and

performing a surface treatment which etches the barrier metal film on asurface of the substrate with a diluent gas plasma to flatten thebarrier metal film, and removes nitrogen atoms in a superficial layer ofthe barrier metal film by the diluent gas plasma to decrease a nitrogencontent of the superficial layer relative to an interior of a matrix ofthe barrier metal film.

Thus, after a barrier metal film is prepared, the substantial metallayer and the metal nitride layer can be formed with a single-layerthickness. Hence, a barrier metal film having a very small thickness canbe produced, with diffusion of metal being prevented and adhesion to themetal being retained. Consequently, a metal wiring process can bestabilized.

According to the present invention, there is also provided a metal filmproduction method comprising:

performing a surface treatment which generates a diluent gas plasmawithin a chamber accommodating a substrate having a barrier metal filmof a metal nitride formed thereon, to etch the barrier metal film on asurface of the substrate with the diluent gas plasma, thereby flatteningthe barrier metal film;

then supplying a source gas containing a halogen into the chamber;

converting an atmosphere within the chamber into a plasma to generate asource gas plasma so that an etched member made of a metal is etchedwith the source gas plasma to form a precursor within the chamber from ametal component contained in the etched member and the source gas; and

making a temperature of the substrate lower than a temperature of theetched member to form the metal component of the precursor as a film onthe substrate having the barrier metal film flattened.

Thus, a metal can be formed as a film through the production of abarrier metal film subjected to a treatment for preventing diffusion ofmetal and retaining adhesion to the metal. Consequently, a metal wiringprocess can be stabilized.

According to the present invention, there is also provided a metal filmproduction method comprising:

performing a surface treatment which generates a diluent gas plasmawithin a chamber accommodating a substrate having a barrier metal filmof a metal nitride formed thereon, to etch the barrier metal film on asurface of the substrate with the diluent gas plasma, thereby flatteningthe barrier metal film, and removes nitrogen atoms in a superficiallayer of the barrier metal film by the diluent gas plasma to decrease anitrogen content of the superficial layer relative to an interior of amatrix of the barrier metal film;

then supplying a source gas containing a halogen into the chamber;

converting an atmosphere within the chamber into a plasma to generate asource gas plasma so that an etched member made of a metal is etchedwith the source gas plasma to form a precursor within the chamber from ametal component contained in the etched member and the source gas; and

making a temperature of the substrate lower than a temperature of theetched member to form the metal component of the precursor as a film onthe substrate having the barrier metal film flattened and having thenitrogen content of the superficial layer relatively decreased.

Thus, the substantial metal layer and the metal nitride layer can beformed with a single-layer thickness. Hence, a metal can be formed as afilm through the production of a barrier metal film having a very smallthickness while preventing diffusion of metal and retaining adhesion tothe metal. Consequently, a metal wiring process can be stabilized.

The metal film production method may further comprise applying adensification treatment for densifying metal atoms in a superficiallayer of the barrier metal film after flattening the barrier metal filmand also relatively decreasing the nitrogen content of the superficiallayer.

Thus, diffusion of the component of the metal film can be preventedreliably.

In the metal film production method, the diluent gas plasma may be anargon gas plasma. Thus, the treatment can be performed reliably with theuse of an inexpensive gas.

According to the present invention, there is also provided a metal filmproduction apparatus, comprising:

a chamber accommodating a substrate;

a metallic etched member provided in the chamber at a position opposedto the substrate;

halogen gas supply means for supplying a source gas containing a halogento an interior of the chamber between the substrate and the etchedmember;

barrier plasma generation means which converts an atmosphere within thechamber into a plasma to generate a source gas plasma so that the etchedmember is etched with the source gas plasma to form a precursor from ametal component contained in the etched member and the source gas;

excitation means for exciting a gas containing nitrogen in a mannerisolated from the chamber;

formation means for forming a metal nitride upon reaction betweennitrogen excited by the excitation means and the precursor;

control means which makes a temperature of the substrate lower than atemperature of the formation means to form the metal nitride as a filmon the substrate for use as a barrier metal film;

diluent gas supply means for supplying a diluent gas to a site above asurface of the substrate; and

surface treatment plasma generation means which converts the atmospherewithin the chamber into a plasma to generate a diluent gas plasma sothat the barrier metal film on the surface of the substrate is etchedwith the diluent gas plasma to flatten the barrier metal film.

Thus, there can be produced a barrier metal film subjected to treatmentfor preventing diffusion of metal and retaining adhesion to the metal.Consequently, a metal wiring process can be stabilized.

According to the present invention, there is also provided a metal filmproduction apparatus, comprising:

a chamber accommodating a substrate;

a metallic etched member provided in the chamber at a position opposedto the substrate;

halogen gas supply means for supplying a source gas containing a halogento an interior of the chamber between the substrate and the etchedmember;

barrier plasma generation means which converts an atmosphere within thechamber into a plasma to generate a source gas plasma so that the etchedmember is etched with the source gas plasma to form a precursor from ametal component contained in the etched member and the source gas;

excitation means for exciting a gas containing nitrogen in a mannerisolated from the chamber;

formation means for forming a metal nitride upon reaction betweennitrogen excited by the excitation means and the precursor;

control means which makes a temperature of the substrate lower than atemperature of the formation means to form the metal nitride as a filmon the substrate for use as a barrier metal film;

diluent gas supply means for supplying a diluent gas to a site above asurface of the substrate; and

surface treatment plasma generation means for performing a surfacetreatment which converts the atmosphere within the chamber into a plasmato generate a diluent gas plasma so that the barrier metal film on thesurface of the substrate is etched with the diluent gas plasma toflatten the barrier metal film, and removes nitrogen atoms in asuperficial layer of the barrier metal film to decrease a nitrogencontent of the superficial layer relative to an interior of a matrix ofthe barrier metal film.

Thus, the substantial metal layer and the metal nitride layer can beformed with a single-layer thickness. Hence, a barrier metal film havinga very small thickness can be produced, with diffusion of metal beingprevented and adhesion to the metal being retained. Consequently, ametal wiring process can be stabilized.

According to the present invention, there is also provided a metal filmproduction apparatus, comprising:

a chamber accommodating a substrate having a barrier metal film of ametal nitride formed thereon;

diluent gas supply means for supplying a diluent gas to an interior ofthe chamber above a surface of the substrate;

surface treatment plasma generation means which converts an atmospherewithin the chamber into a plasma to generate a diluent gas plasma sothat the barrier metal film on the surface of the substrate is etchedwith the diluent gas plasma to flatten the barrier metal film;

a metallic etched member provided in the chamber;

source gas supply means for supplying a source gas containing a halogento an interior of the chamber between the substrate and the etchedmember;

plasma generation means which converts the source gas containing thehalogen into a plasma to generate a source gas plasma so that the etchedmember is etched with the source gas plasma to form a precursor from ametal component contained in the etched member and the source gas; and

control means which makes a temperature of the substrate lower than atemperature of the etched member to form the metal component of theprecursor as a film on the flattened barrier metal film.

Thus, a metal film can be formed through the production of a barriermetal film subjected to a treatment for preventing diffusion of metaland retaining adhesion to the metal. Consequently, a metal wiringprocess can be stabilized.

According to the present invention, there is also provided a metal filmproduction apparatus, comprising:

a chamber accommodating a substrate having a barrier metal film of ametal nitride formed thereon;

diluent gas supply means for supplying a diluent gas to an interior ofthe chamber above a surface of the substrate;

surface treatment plasma generation means which converts an atmospherewithin the chamber into a plasma to generate a diluent gas plasma sothat the barrier metal film on the surface of the substrate is etchedwith the diluent gas plasma to flatten the barrier metal film, and alsoremoves nitrogen atoms in a superficial layer of the barrier metal filmby the diluent gas plasma to decrease a nitrogen content of thesuperficial layer relative to an interior of a matrix of the barriermetal film;

a metallic etched member provided in the chamber;

source gas supply means for supplying a source gas containing a halogento an interior of the chamber between the substrate and the etchedmember;

plasma generation means which converts the source gas containing thehalogen into a plasma to generate a source gas plasma so that the etchedmember is etched with the source gas plasma to form a precursor from ametal component contained in the etched member and the source gas; and

control means which makes a temperature of the substrate lower than atemperature of the etched member to form the metal component of theprecursor as a film on the barrier metal film flattened and having thenitrogen content of the superficial layer relatively decreased.

Thus, the substantial metal layer and the metal nitride layer can beformed with a single-layer thickness. Hence, a metal film can be formedthrough the production of a barrier metal film having a very smallthickness while preventing diffusion of metal and retaining adhesion tothe metal. Consequently, a metal wiring process can be stabilized.

The metal film production apparatus may further comprise densificationtreatment means for densifying metal atoms in the superficial layerafter flattening the barrier metal film and also relatively decreasingthe nitrogen content of the superficial layer. Thus, diffusion of thecomponent of the metal film can be prevented reliably.

In the metal film production apparatus, the diluent gas plasma may be anargon gas plasma. Thus, the treatment can be performed reliably with theuse of an inexpensive gas.

According to the present invention, there is also provided a metal filmformed by flattening a barrier metal film of a metal nitride on asurface of a substrate by etching with a diluent gas plasma.

Thus, the resulting metal film has a barrier metal film retainingadhesion, and can stabilize a metal wiring process.

According to the present invention, there is also provided a metal filmformed by a surface treatment which flattens a barrier metal film of ametal nitride on a surface of a substrate by etching with a diluent gasplasma, and removes nitrogen atoms in a superficial layer of the barriermetal film by the diluent gas plasma to decrease a nitrogen content ofthe superficial layer relative to an interior of a matrix of the barriermetal film.

Thus, there is obtained a metal film which has a barrier metal filmcomprising the substantial metal layer and the metal nitride layerformed with a single-layer thickness, and produced with a very smallthickness, with diffusion of metal being prevented and adhesion to themetal being retained, and which can stabilize a metal wiring process.

According to the present invention, there is also provided a metal filmproduction method involving treatment of a surface of a substrate havinga barrier metal film of a metal nitride formed thereon, comprising:

performing a surface treatment which reacts the barrier metal film onthe surface of the substrate in a reducing gas atmosphere to removenitrogen atoms in a superficial layer of the barrier metal film, therebydecreasing a nitrogen content of the superficial layer relative to aninterior of a matrix of the barrier metal film.

Thus, a barrier metal film with a very small thickness and comprisingthe substantial metal layer and the metal nitride layer formed with asingle-layer thickness can be produced, with diffusion of metal beingprevented and adhesion to the metal being retained. Consequently, ametal wiring process can be stabilized.

According to the present invention, there is also provided a metal filmproduction method comprising:

supplying a source gas containing a halogen to an interior of a chamberbetween a substrate and a metallic etched member;

converting an atmosphere within the chamber into a plasma to generate asource gas plasma so that the etched member is etched with the sourcegas plasma to form a precursor from a metal component contained in theetched member and the source gas, and also exciting a gas containingnitrogen in a manner isolated from the chamber accommodating thesubstrate;

forming a metal nitride upon reaction between excited nitrogen and theprecursor;

making a temperature of the substrate lower than a temperature of meansfor formation of the metal nitride to form the metal nitride as a filmon the substrate for use as a barrier metal film; and

performing a surface treatment which reacts the barrier metal film on asurface of the substrate in a reducing gas atmosphere to remove nitrogenatoms in a superficial layer of the barrier metal film, therebydecreasing a nitrogen content of the superficial layer relative to aninterior of a matrix of the barrier metal film.

Thus, a barrier metal film with a very small thickness and comprisingthe substantial metal layer and the metal nitride layer formed with asingle-layer thickness can be produced, with diffusion of metal beingprevented and adhesion to the metal being retained. Consequently, ametal wiring process can be stabilized.

According to the present invention, there is also provided a metal filmproduction method comprising:

performing a surface treatment in a chamber accommodating a substratehaving a barrier metal film of a metal nitride formed thereon, saidsurface treatment comprising reacting the barrier metal film on asurface of the substrate in a reducing gas atmosphere to remove nitrogenatoms in a superficial layer of the barrier metal film, therebydecreasing a nitrogen content of the superficial layer relative to aninterior of a matrix of the barrier metal film;

then supplying a source gas containing a halogen into the chamber;

converting an atmosphere within the chamber into a plasma to generate asource gas plasma so that a metallic etched member is etched with thesource gas plasma to form a precursor within the chamber from a metalcomponent contained in the etched member and the source gas; and

making a temperature of the substrate lower than a temperature of theetched member to form the metal component of the precursor as a film onthe substrate having the barrier metal film flattened thereon.

Thus, a metal film can be formed through the production of a barriermetal film having a very small thickness and comprising the substantialmetal layer and the metal nitride layer formed with a single-layerthickness, while preventing diffusion of metal and retaining adhesion tothe metal. Consequently, a metal wiring process can be stabilized.

According to the present invention, there is also provided a metal filmproduction apparatus, comprising:

a chamber accommodating a substrate;

a metallic etched member provided in the chamber at a position opposedto the substrate;

halogen gas supply means for supplying a source gas containing a halogento an interior of the chamber between the substrate and the etchedmember;

barrier plasma generation means which converts an atmosphere within thechamber into a plasma to generate a source gas plasma so that the etchedmember is etched with the source gas plasma to form a precursor from ametal component contained in the etched member and the source gas;

excitation means for exciting a gas containing nitrogen in a mannerisolated from the chamber;

formation means for forming a metal nitride upon reaction betweennitrogen excited by the excitation means and the precursor;

control means which makes a temperature of the substrate lower than atemperature of the formation means to form the metal nitride as a filmon the substrate for use as a barrier metal film;

reducing gas supply means for supplying a reducing gas to a site above asurface of the substrate; and

surface treatment means which reacts the barrier metal film on thesurface of the substrate in a reducing gas atmosphere to remove nitrogenatoms in a superficial layer of the barrier metal film, therebydecreasing a nitrogen content of the superficial layer relative to aninterior of a matrix of the barrier metal film.

Thus, a barrier metal film with a very small thickness and comprisingthe substantial metal layer and the metal nitride layer formed with asingle-layer thickness can be produced, with diffusion of metal beingprevented and adhesion to the metal being retained. Consequently, ametal wiring process can be stabilized.

According to the present invention, there is also provided a metal filmproduction apparatus, comprising:

a chamber accommodating a substrate having a barrier metal film of ametal nitride formed thereon;

reducing gas supply means for supplying a reducing gas to a site above asurface of the substrate;

surface treatment means which reacts the barrier metal film on thesurface of the substrate in a reducing gas atmosphere to remove nitrogenatoms in a superficial layer of the barrier metal film, therebydecreasing a nitrogen content of the superficial layer relative to aninterior of a matrix of the barrier metal film;

a metallic etched member provided in the chamber;

source gas supply means for supplying a source gas containing a halogento an interior of the chamber between the substrate and the etchedmember;

plasma generation means which converts the source gas containing thehalogen into a plasma to generate a source gas plasma so that the etchedmember is etched with the source gas plasma to form a precursor from ametal component contained in the etched member and the source gas; and

control means which makes a temperature of the substrate lower than atemperature of the etched member to form the metal component of theprecursor as a film on the barrier metal film having the nitrogencontent of the superficial layer relatively decreased.

Thus, a metal film can be formed through the production of a barriermetal film having a very small thickness and comprising the substantialmetal layer and the metal nitride layer formed with a single-layerthickness, while preventing diffusion of metal and retaining adhesion tothe metal. Consequently, a metal wiring process can be stabilized.

According to the present invention, there is also provided a metal filmformed by a surface treatment which reacts a barrier metal film of ametal nitride on a surface of a substrate in a reducing gas atmosphereto remove nitrogen atoms in a superficial layer of the barrier metalfilm, thereby decreasing a nitrogen content of the superficial layerrelative to an interior of a matrix of the barrier metal film.

Thus, there is obtained a metal film which has a barrier metal filmcomprising the substantial metal layer and the metal nitride layerformed with a single-layer thickness, and produced with a very smallthickness, with diffusion of metal being prevented and adhesion to themetal being retained, and which can stabilize a metal wiring process.

According to the present invention, there is also provided a metal filmproduction method involving treatment of a surface of a substrate havinga barrier metal film of a metal nitride formed thereon, comprising:

performing a surface treatment which forms nuclei of silicon atoms on asurface of the barrier metal film on the surface of the substrate by agas plasma containing silicon.

Thus, a barrier metal film with a very small thickness can be produced,with adhesion to metal being retained. Consequently, a metal wiringprocess can be stabilized.

According to the present invention, there is also provided a metal filmproduction method comprising:

supplying a source gas containing a halogen to an interior of a chamberbetween a substrate and a metallic etched member;

converting an atmosphere within the chamber into a plasma to generate asource gas plasma so that the etched member is etched with the sourcegas plasma to form a precursor from a metal component contained in theetched member and the source gas, and also exciting a gas containingnitrogen in a manner isolated from the chamber accommodating thesubstrate;

forming a metal nitride upon reaction between excited nitrogen and theprecursor;

making a temperature of the substrate lower than a temperature of meansfor formation of the metal nitride to form the metal nitride as a filmon the substrate for use as a barrier metal film; and

performing a surface treatment which forms nuclei of silicon atoms on asurface of the barrier metal film on a surface of the substrate by a gasplasma containing silicon.

Thus, a barrier metal film with a very small thickness can be produced,with adhesion to metal being retained. Consequently, a metal wiringprocess can be stabilized.

According to the present invention, there is also provided a metal filmproduction method comprising:

performing a surface treatment in a chamber accommodating a substratehaving a barrier metal film of a metal nitride formed thereon, saidsurface treatment comprising forming nuclei of silicon atoms on asurface of the barrier metal film on a surface of the substrate by a gasplasma containing silicon;

then supplying a source gas containing a halogen into the chamber;

converting an atmosphere within the chamber into a plasma to generate asource gas plasma so that a metallic etched member is etched with thesource gas plasma to form a precursor within the chamber from a metalcomponent contained in the etched member and the source gas; and

making a temperature of the substrate lower than a temperature of theetched member to form the metal component of the precursor as a film onthe substrate having the nuclei of silicon atoms formed on the surfaceof the barrier metal film.

Thus, a metal film can be formed through the production of a barriermetal film having a very small thickness and retaining adhesion tometal. Consequently, a metal wiring process can be stabilized.

According to the present invention, there is also provided a metal filmproduction apparatus, comprising:

a chamber accommodating a substrate;

a metallic etched member provided in the chamber at a position opposedto the substrate;

halogen gas supply means for supplying a source gas containing a halogento an interior of the chamber between the substrate and the etchedmember;

barrier plasma generation means which converts an atmosphere within thechamber into a plasma to generate a source gas plasma so that the etchedmember is etched with the source gas plasma to form a precursor from ametal component contained in the etched member and the source gas;

excitation means for exciting a gas containing nitrogen in a mannerisolated from the chamber;

formation means for forming a metal nitride upon reaction betweennitrogen excited by the excitation means and the precursor;

control means which makes a temperature of the substrate lower than atemperature of the formation means to form the metal nitride as a filmon the substrate for use as a barrier metal film;

silicon-containing gas supply means for supplying a gas containingsilicon to a site above a surface of the substrate; and

surface treatment plasma generation means which generates a gas plasmacontaining silicon to form nuclei of silicon atoms on a surface of thebarrier metal film on the surface of the substrate.

Thus, a barrier metal film with a very small thickness can be produced,with adhesion to metal being retained. Consequently, a metal wiringprocess can be stabilized.

According to the present invention, there is also provided a metal filmproduction apparatus, comprising:

a chamber accommodating a substrate having a barrier metal film of ametal nitride formed thereon;

silicon-containing gas supply means for supplying a gas containingsilicon to a site above a surface of the substrate;

surface treatment plasma generation means which generates a gas plasmacontaining silicon to form nuclei of silicon atoms on a surface of thebarrier metal film on the surface of the substrate;

a metallic etched member provided in the chamber;

source gas supply means for supplying a source gas containing a halogento an interior of the chamber between the substrate and the etchedmember;

plasma generation means which converts the source gas containing thehalogen into a plasma to generate a source gas plasma so that the etchedmember is etched with the source gas plasma to form a precursor from ametal component contained in the etched member and the source gas; and

control means which makes a temperature of the substrate lower than atemperature of the etched member to form the metal component of theprecursor as a film on the barrier metal film having the nuclei ofsilicon atoms formed on the surface thereof.

Thus, a metal film can be formed through the production of a barriermetal film having a very small thickness and retaining adhesion tometal. Consequently, a metal wiring process can be stabilized.

According to the present invention, there is also provided a metal filmformed by applying a surface treatment to a barrier metal film of ametal nitride on a surface of a substrate such that nuclei of siliconatoms are formed on a surface of the barrier metal film on the surfaceof the substrate by a gas plasma containing silicon.

Thus, there is obtained a metal film which has a barrier metal filmhaving a very small thickness and retaining adhesion to metal, and whichcan stabilize a metal wiring process.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will become more fully understood from thedetailed description given hereinbelow and the accompanying drawingswhich are given by way of illustration only, and thus are not limitativeof the present invention, and wherein:

FIG. 1 is a schematic side view of a barrier metal film productionapparatus according to a first embodiment of the present invention;

FIG. 2 is a detail view of a substrate on which a barrier metal film hasbeen produced;

FIG. 3 is a schematic side view of a barrier metal film productionapparatus according to a second embodiment of the present invention;

FIG. 4 is a view taken along the arrowed line IV-IV of FIG. 3;

FIG. 5 is a view taken along the arrowed line V-V of FIG. 4;

FIG. 6 is a schematic side view of a barrier metal film productionapparatus according to a third embodiment of the present invention;

FIG. 7 is a schematic side view of a barrier metal film productionapparatus according to a fourth embodiment of the present invention;

FIG. 8 is a schematic side view of a barrier metal film productionapparatus according to a fifth embodiment of the present invention;

FIG. 9 is a schematic side view of a barrier metal film productionapparatus according to a sixth embodiment of the present invention;

FIG. 10 is a schematic side view of a barrier metal film productionapparatus according to a seventh embodiment of the present invention;

FIG. 11 is a schematic side view of a barrier metal film productionapparatus according to an eighth embodiment of the present invention;

FIG. 12 is a schematic side view of a barrier metal film productionapparatus according to a ninth embodiment of the present invention;

FIG. 13 is a sectional view of a substrate illustrating a barrier metalfilm;

FIG. 14 is a concept view of a barrier metal film in a treatment fordenitrification;

FIG. 15 is a concept view of the barrier metal film in the treatment fordenitrification;

FIG. 16 is a concept view of a barrier metal film in a treatment foroxide layer formation;

FIG. 17 is a graph representing the relationship between the contactangle of copper particles and the oxygen concentration of the substrate;

FIG. 18 is a concept view of a barrier metal film in a treatment forhydroxyl group formation;

FIG. 19 is a schematic construction drawing showing another example ofdiluent gas supply means;

FIG. 20 is a schematic construction drawing of a barrier metal filmproduction apparatus according to a tenth embodiment of the presentinvention;

FIG. 21 is a concept view of an example of production of a barrier metalfilm by the barrier metal film production apparatus according to thetenth embodiment of the present invention;

FIG. 22 is a schematic side view of a barrier metal film productionapparatus according to an eleventh embodiment of the present invention;

FIG. 23 is a schematic side view of a barrier metal film productionapparatus according to a twelfth embodiment of the present invention;

FIG. 24 is a view taken along the arrowed line XIII-XIII of FIG. 23;

FIG. 25 is a view taken along the arrowed line XIV-XIV of FIG. 24;

FIG. 26 is a schematic side view of a barrier metal film productionapparatus according to a thirteenth embodiment of the present invention;

FIG. 27 is a schematic side view of a barrier metal film productionapparatus according to a fourteenth embodiment of the present invention;

FIG. 28 is an outline drawing of an apparatus for a film formationprocess;

FIG. 29 is a schematic side view of a metal film production apparatusaccording to a fifteenth embodiment of the present invention;

FIG. 30 is a schematic construction drawing showing another example ofdiluent gas supply means;

FIG. 31 is a sectional view of a substrate illustrating a barrier metalfilm;

FIG. 32 is a concept view of a barrier metal film in a treatment fordenitrification;

FIG. 33 is a concept view of the barrier metal film in the treatment fordenitrification;

FIG. 34 is a schematic side view of a metal film production apparatusaccording to a sixteenth embodiment of the present invention;

FIG. 35 is a view taken along the arrowed line VIII-VIII of FIG. 34;

FIG. 36 is a view taken along the arrowed line IX-IX of FIG. 35;

FIG. 37 is a schematic side view of a metal film production apparatusaccording to a seventeenth embodiment of the present invention;

FIG. 38 is a schematic side view of a metal film production apparatusaccording to an eighteenth embodiment of the present invention;

FIG. 39 is a schematic side view of a metal film production apparatusaccording to a nineteenth embodiment of the present invention;

FIG. 40 is a conceptual construction drawing of a metal film productionapparatus according to a twentieth embodiment of the present invention;

FIG. 41 is a concept view of a barrier metal film in a treatment fordenitrification;

FIG. 42 is a schematic construction drawing of a metal film productionapparatus according to a twenty-first embodiment of the presentinvention; and

FIG. 43 is a concept view of a barrier metal film in formation of nucleiof Si.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The first embodiment of the barrier metal film production apparatus andbarrier metal film production method of the present invention will bedescribed with reference to FIGS. 1 and 2. FIG. 1 is a schematic sideview of the barrier metal film production apparatus according to thefirst embodiment of the present invention. FIG. 2 shows details of asubstrate on which a barrier metal film has been prepared.

As shown in the drawings, a support platform 2 is provided near thebottom of a cylindrical chamber 1 made of, say, a ceramic (an insulatingmaterial), and a substrate 3 is placed on the support platform 2.Temperature control means 6 equipped with a heater 4 and refrigerantflow-through means 5 is provided in the support platform 2 so that thesupport platform 2 is controlled to a predetermined temperature (forexample, a temperature at which the substrate 3 is maintained at 100 to200° C.) by the temperature control means 6.

An upper surface of the chamber 1 is an opening, which is closed with ametal member 7, as an etched member, made of a metal (e.g., W, Ti, Ta,or TiSi). The interior of the chamber 1 closed with the metal member 7is maintained at a predetermined pressure by a vacuum device 8. A plasmaantenna 9, as a coiled winding antenna 9 of plasma generation means, isprovided around a cylindrical portion of the chamber 1. A matchinginstrument 10 and a power source 11 are connected to the plasma antenna9 to supply power.

Nozzles 12 for supplying a source gas (a Cl₂ gas diluted with He or Arto a chlorine concentration of ≦50%, preferably about 10%), containingchlorine as a halogen, to the interior of the chamber 1 are connected tothe cylindrical portion of the chamber 1 below the metal member 7. Thenozzle 12 is open toward the horizontal, and is fed with the source gasvia a flow controller 13. Fluorine (F), bromine (Br) or iodine (I) canalso be applied as the halogen to be incorporated into the source gas.

Slit-shaped opening portions 14 are formed at a plurality of locations(for example, four locations) in the periphery of a lower part of thecylindrical portion of the chamber 1, and one end of a tubular passage15 is fixed to each of the opening portions 14. A tubular excitationchamber 16 made of an insulator is provided halfway through the passage15, and a coiled plasma antenna 17 is provided around the excitationchamber 16. The plasma antenna 17 is connected to a matching instrument18 and a power source 19 to receive power. The plasma antenna 17, thematching instrument 18 and the power source 19 constitute excitationmeans. A flow controller 20 is connected to the other end of the passage15, and an ammonia gas (NH₃ gas) as a nitrogen-containing gas issupplied into the passage 15 via the flow controller 20.

With the above-described barrier metal film production apparatus, thesource gas is supplied through the nozzles 12 to the interior of thechamber 1, and electromagnetic waves are shot from the plasma antenna 9into the chamber 1. As a result, the Cl₂ gas is ionized to generate aCl₂ gas plasma (source gas plasma) 21. The Cl₂ gas plasma 21 causes anetching reaction to the metal member 7, forming a precursor(M_(x)Cl_(y): M is a metal such as W, Ti, Ta or TiSi) 22.

Separately, the NH₃ gas is supplied into the passage 15 via the flowcontroller 20 and fed into the excitation chamber 16. By shootingelectromagnetic waves from the plasma antenna 17 into the excitationchamber 16, the NH₃ gas is ionized to generate an NH₃ gas plasma 23.Since a predetermined differential pressure has been established betweenthe pressure inside the chamber 1 and the pressure inside the excitationchamber 16 by the vacuum device 8, the excited ammonia of the NH₃ gasplasma 23 in the excitation chamber 16 is fed to the precursor(M_(x)Cl_(y)) 22 inside the chamber 1 through the opening portion 14.

That is, excitation means for exciting the nitrogen-containing gas inthe excitation chamber 16 isolated from the chamber 1 is constructed.Because of this construction, the metal component of the precursor(M_(x)Cl_(y)) 22 and ammonia react to form a metal nitride (MN) (i.e.,formation means). At this time, the metal member 7 and the excitationchamber 16 are maintained by the plasmas at predetermined temperatures(e.g., 200 to 400° C.) which are higher than the temperature of thesubstrate 3.

The metal nitride (MN) formed within the chamber 1 is transported towardthe substrate 3 controlled to a low temperature, whereby a thin MN film24 is formed on the surface of the substrate 3. After the thin MN film24 is formed, the supply of the NH₃ gas and the supply of power to thepower source 19 are cut off. Thus, the precursor (M_(x)Cl_(y)) 22 istransported toward the substrate 3 controlled to a lower temperaturethan the temperature of the metal member 7. The precursor (M_(x)Cl_(y))22 transported toward the substrate 3 is converted into only metal (M)ions by a reduction reaction, and directed at the substrate 3 to form athin M film 25 on the thin MN film 24 on the substrate 3. A barriermetal film 26 is composed of the thin MN film 24 and the thin M film 25(see FIG. 2).

The reaction for formation of the thin MN film 24 can be expressed by:

2MCl+2NH₃→2MN↓+HCl↑+2H₂↑

The reaction for formation of the thin M film 25 can be expressed by:

2MCl→2M↓+Cl₂↑

The gases and the etching products that have not been involved in thereactions are exhausted through an exhaust port 27.

The source gas has been described, with the Cl₂ gas diluted with, say,He or Ar taken as an example. However, the Cl₂ gas can be used alone, oran HCl gas can also be applied. If the HCl gas is applied, an HCl gasplasma is generated as the source gas plasma. Thus, the source gas maybe any gas containing chlorine, and a gas mixture of an HCl gas and aCl₂ gas is also usable. As the material for the metal member 7, it ispossible to use an industrially applicable metal such as Ag, Au, Pt orSi.

The substrate 3, on which the barrier metal film 26 has been formed, issubjected to a film forming device, which forms a thin copper (Cu) filmor a thin aluminum (Al) film on the barrier metal film 26. Because ofthe presence of the barrier metal film 26, there arise advantages, forexample, such that the thin MN film 24 eliminates diffusion of Cu intothe substrate 3, and the thin M film 25 ensures adhesion of Cu.

If the material to be formed as a film is a material unproblematic interms of adhesion (e.g., Al), or if it is a metal to which the nitridecan retain adhesion, the thin M film 25 can be omitted from the barriermetal film 26. Furthermore, the reduction reaction is caused by thetemperature difference. However, a reducing gas plasma can be generatedseparately to produce a reduction reaction.

With the above-described barrier metal film production apparatus, themetal is formed by plasmas to produce the barrier metal film 26. Thus,the barrier metal film 26 can be formed uniformly to a small thickness.Consequently, the barrier metal film 26 can be formed highly accuratelyat a high speed with excellent burial properties in a very smallthickness even to the interior of a tiny depression, for example severalhundred nanometers wide, which has been provided in the substrate 3.

A barrier metal film production apparatus and a barrier metal filmproduction method according to the second embodiment of the presentinvention will be described with reference to FIGS. 3 to 5. FIG. 3 is aschematic side view of the barrier metal film production apparatusaccording to the second embodiment of the present invention. FIG. 4 is aview taken along the arrowed line IV-IV of FIG. 3. FIG. 5 is a viewtaken along the arrowed line V-V of FIG. 4. The same members as themembers illustrated in FIG. 1 are assigned the same numerals, andduplicate explanations are omitted.

An upper surface of the chamber 1 is an opening, which is closed with adisk-shaped ceiling board 30 made of an insulating material (forexample, a ceramic). An etched member 31 made of a metal (e.g., W, Ti,Ta or TiSi) is interposed between the opening at the upper surface ofthe chamber 1 and the ceiling board 30. The etched member 31 is providedwith a ring portion 32 fitted into the opening at the upper surface ofthe chamber 1. A plurality of (12 in the illustrated embodiment)protrusions 33, which extend close to the center in the diametricaldirection of the chamber 1 and have the same width, are provided in thecircumferential direction on the inner periphery of the ring portion 32.

The protrusions 33 are integrally or removably attached to the ringportion 32. Notches (spaces) 35 formed between the protrusions 33 arepresent between the ceiling board 30 and the interior of the chamber 1.The ring portion 32 is earthed, and the plural protrusions 33 areelectrically connected together and maintained at the same potential.Temperature control means (not shown), such as a heater, is provided inthe etched member 31 to control the temperature of the etched member 31to 200 to 400° C., for example.

Second protrusions shorter in the diametrical direction than theprotrusions 33 can be arranged between the protrusions 33. Moreover,short protrusions can be arranged between the protrusion 33 and thesecond protrusion. By so doing, the area of copper, an object to beetched, can be secured, with an induced current being suppressed.

A planar winding-shaped plasma antenna 34, for converting the atmosphereinside the chamber 1 into a plasma, is provided above the ceiling board30. The plasma antenna 34 is formed in a planar ring shape parallel tothe surface of the ceiling board 30. A matching instrument 10 and apower source 11 are connected to the plasma antenna 34 to supply power.The etched member 31 has the plurality of protrusions 33 provided in thecircumferential direction on the inner periphery of the ring portion 32,and includes the notches (spaces) 35 formed between the protrusions 33.Thus, the protrusions 33 are arranged between the substrate 3 and theceiling board 30 in a discontinuous state relative to the flowingdirection of electricity in the plasma antenna 34.

With the above-described barrier metal film production apparatus, thesource gas is supplied through the nozzles 12 to the interior of thechamber 1, and electromagnetic waves are shot from the plasma antenna 34into the chamber 1. As a result, the Cl₂ gas is ionized to generate aCl₂ gas plasma (source gas plasma) 21. The etched member 31, an electricconductor, is present below the plasma antenna 34. However, the Cl₂ gasplasma 21 occurs stably between the etched member 31 and the substrate3, namely, below the etched member 31, under the following action:

The action by which the Cl₂ gas plasma 21 is generated below the etchedmember 31 will be described. As shown in FIG. 5, a flow A of electricityin the plasma antenna 34 of the planar ring shape crosses theprotrusions 33. At this time, an induced current B occurs on the surfaceof the protrusion 33 opposed to the plasma antenna 34. Since the notches(spaces) 35 are present in the etched member 31, the induced current Bflows onto the lower surface of each protrusion 33, forming a flow a inthe same direction as the flow A of electricity in the plasma antenna 34(Faraday shield).

When the etched member 31 is viewed from the substrate 3, therefore,there is no flow in a direction in which the flow A of electricity inthe plasma antenna 34 is canceled out. Furthermore, the ring portion 32is earthed, and the protrusions 33 are maintained at the same potential.Thus, even though the etched member 31, an electric conductor, exists,the electromagnetic wave is reliably thrown from the plasma antenna 34into the chamber 1. Consequently, the Cl₂ gas plasma 21 is stablygenerated below the etched member 31.

Furthermore, plasma generation means composed of a passage 15, anexcitation chamber 16 and a plasma antenna 17 is provided above thesupport platform 2.

The Cl₂ gas plasma 21 causes an etching reaction to the etched member31, forming a precursor (M_(x)Cl_(y): M is a metal such as W, Ti, Ta orTiSi) 22. In the excitation chamber 16, the NH₃ gas is ionized togenerate an NH₃ gas plasma 23. The excited ammonia of the NH₃ gas plasma23 in the excitation chamber 16 is fed to the precursor (M_(x)Cl_(y)) 22inside the chamber 1 through the opening portion 14. Because of thisconstruction, the metal component of the precursor (M_(x)Cl_(y)) 22 andammonia react to form a metal nitride (MN) (formation means). At thistime, the etched member 31 and the excitation chamber 16 are maintainedby the plasmas at predetermined temperatures (e.g., 200 to 400° C.)which are higher than the temperature of the substrate 3.

The metal nitride (MN) formed within the chamber 1 is transported towardthe substrate 3 controlled to a low temperature, whereby a thin MN film24 is formed on the surface of the substrate 3. After the thin MN film24 is formed, the supply of the NH₃ gas and the supply of power to thepower source 19 are cut off. Thus, the precursor (M_(x)Cl_(y)) 22 istransported toward the substrate 3 controlled to a lower temperaturethan the temperature of the etched member 31. The precursor(M_(x)Cl_(y)) 22 transported toward the substrate 3 is converted intoonly metal (M) ions by a reduction reaction, and directed at thesubstrate 3 to form a thin M film 25 on the thin MN film 24 on thesubstrate 3. A barrier metal film 26 is composed of the thin MN film 24and the thin M film 25 (see FIG. 2). The gases and the etching products,which have not been involved in the reactions, are exhausted through anexhaust port 27.

With the above-described barrier metal film production apparatus,similar to the first embodiment, the metal is formed by plasmas toproduce the barrier metal film 26. Thus, the barrier metal film 26 canbe formed uniformly to a small thickness. Consequently, the barriermetal film 26 can be formed highly accurately at a high speed withexcellent burial properties in a very small thickness even to theinterior of a tiny depression, for example several hundred nanometerswide, which has been provided in the substrate 3.

In addition, the etched member 31 has the plurality of protrusions 33provided in the circumferential direction on the inner periphery of thering portion 32, and includes the notches (spaces) 35 formed between theprotrusions 33. Thus, the induced currents generated in the etchedmember 31 flow in the same direction as the flowing direction ofelectricity in the plasma antenna 34, when viewed from the substrate 3.Therefore, even though the etched member 31, an electric conductor,exists below the plasma antenna 34, the electromagnetic waves arereliably thrown from the plasma antenna 34 into the chamber 1.Consequently, the Cl₂ gas plasma 21 can be stably generated below theetched member 31.

A barrier metal film production apparatus and a barrier metal filmproduction method according to the third embodiment of the presentinvention will be described with reference to FIG. 6. FIG. 6 is aschematic side view of the barrier metal film production apparatusaccording to the third embodiment of the present invention. The samemembers as the members illustrated in FIGS. 1 and 3 are assigned thesame numerals, and duplicate explanations are omitted.

The opening of an upper portion of the chamber 1 is closed with aceiling board 30, for example, made of a ceramic (an insulatingmaterial). An etched member 41 made of a metal (e.g., W, Ti, Ta or TiSi)is provided on a lower surface of the ceiling board 30, and the etchedmember 41 is of a quadrangular pyramidal shape. Slit-shaped secondopening portions 42 are formed at a plurality of locations (for example,four locations) in the periphery of an upper part of the cylindricalportion of the chamber 1, and one end of a tubular second passage 43 isfixed to the second opening portion 42.

A tubular second excitation chamber 44 made of an insulator is providedhalfway through the second passage 43, and a coiled second plasmaantenna 45 is provided around the second excitation chamber 44. Theplasma antenna 45 is connected to a matching instrument 48 and a powersource 49 to receive power. The second plasma antenna 45, the matchinginstrument 48 and the power source 49 constitute plasma generationmeans.

A flow controller 46 is connected to the other end of the second passage43, and a chlorine-containing source gas (a Cl₂ gas diluted with He orAr to a chlorine concentration of ≦50%, preferably about 10%) issupplied into the passage 43 via the flow controller 46. By shootingelectromagnetic waves from the second plasma antenna 45 into the secondexcitation chamber 44, the Cl₂ gas is ionized to generate a Cl₂ gasplasma (source gas plasma) 47. Because of the generation of the Cl₂ gasplasma 47, excited chlorine is fed into the chamber 1 through the secondopening portion 42, whereupon the etched member 41 is etched withexcited chlorine.

With the above-described barrier metal film production apparatus, thesource gas is supplied into the second passage 43 via the flowcontroller 46 and fed into the second excitation chamber 44. By shootingelectromagnetic waves from the second plasma antenna 45 into the secondexcitation chamber 44, the Cl₂ gas is ionized to generate a Cl₂ gasplasma (source gas plasma) 47. Since a predetermined differentialpressure has been established between the pressure inside the chamber 1and the pressure inside the second excitation chamber 44 by the vacuumdevice 8, the excited chlorine of the Cl₂ gas plasma 47 in the secondexcitation chamber 44 is fed to the etched member 41 inside the chamber1 through the second opening portion 42. The excited chlorine causes anetching reaction to the etched member 41, forming a precursor(M_(x)Cl_(y)) 22 inside the chamber 1. At this time, the etched member41 is maintained at a predetermined temperature (e.g., 200 to 400° C.),which is higher than the temperature of the substrate 3, by a heater 50provided in the ceiling board 30.

In the excitation chamber 16, the NH₃ gas is ionized to generate an NH₃gas plasma 23. The excited ammonia of the NH₃ gas plasma 23 in theexcitation chamber 16 is fed to the precursor (M_(x)Cl_(y)) 22 insidethe chamber 1 through the opening portion 14. As a result, the metalcomponent of the precursor (M_(x)Cl_(y)) 22 and ammonia react to form ametal nitride (MN). At this time, the excitation chamber 16 ismaintained by the plasma at a predetermined temperature (e.g., 200 to400° C.) which is higher than the temperature of the substrate 3.

The metal nitride (MN) formed within the chamber 1 is transported towardthe substrate 3 controlled to a low temperature, whereby a thin MN film24 is formed on the surface of the substrate 3. After the thin MN film24 is formed, the supply of the NH₃ gas and the supply of power to thepower source 19 are cut off. Thus, the precursor (M_(x)Cl_(y)) 22 istransported toward the substrate 3 controlled to a lower temperaturethan the temperature of the etched member 41. The precursor(M_(x)Cl_(y)) 22 transported toward the substrate 3 is converted intoonly metal (M) ions by a reduction reaction, and directed at thesubstrate 3 to form a thin M film 25 on the thin MN film 24 placed onthe substrate 3. A barrier metal film 26 is composed of the thin MN film24 and the thin M film 25 (see FIG. 2). The gases and the etchingproducts that have not been involved in the reactions are exhaustedthrough an exhaust port 27.

With the above-described barrier metal film production apparatus,similar to the first embodiment and the second embodiment, the metal isformed by plasmas to produce the barrier metal film 26. Thus, thebarrier metal film 26 can be formed uniformly to a small thickness.Consequently, the barrier metal film 26 can be formed highly accuratelyat a high speed with excellent burial properties in a very smallthickness even to the interior of a tiny depression, for example severalhundred nanometers wide, which has been provided in the substrate 3.

Furthermore, the Cl₂ gas plasma 47 is generated in the second excitationchamber 44 isolated from the chamber 1. Thus, the substrate 3 is notexposed to the plasma any more, and the substrate 3 becomes free fromdamage from the plasma.

As the means for generating the Cl₂ gas plasma 47 in the secondexcitation chamber 44, namely, the means for exciting the source gas toconvert it into an excited source gas, it is possible to use microwaves,laser, electron rays, or synchrotron radiation. It is also permissibleto form the precursor by heating the metal filament to a hightemperature. The construction for isolating the Cl₂ gas plasma 47 fromthe substrate 3 may be the provision of the second excitation chamber 44in the passage 43, as stated above, or may be other construction, forexample, the isolation of the chamber 1.

A barrier metal film production apparatus and a barrier metal filmproduction method according to the fourth embodiment of the presentinvention will be described with reference to FIG. 7. FIG. 7 is aschematic side view of a barrier metal film production apparatusaccording to the fourth embodiment of the present invention. The samemembers as the members illustrated in FIG. 1 are assigned the samenumerals, and duplicate explanations are omitted.

Compared with the barrier metal film production apparatus of the firstembodiment shown in FIG. 1, the plasma antenna 9 is not provided aroundthe cylindrical portion of the chamber 1, and the matching instrument 10and power source 11 are connected to the metal member 7 for supply ofpower to the metal member 7.

With the above-described barrier metal film production apparatus, thesource gas is supplied from the nozzle 12 into the chamber 1, andelectromagnetic waves are shot from the metal member 7 into the chamber1, whereby the Cl₂ gas is ionized to generate a Cl₂ gas plasma (sourcegas plasma) 21. The Cl₂ gas plasma 21 causes an etching reaction to themetal member 7, forming a precursor (M_(x)Cl_(y)) 22. At this time, themetal member 7 is maintained at a temperature (e.g., 200 to 400° C.),which is higher than the temperature of the substrate 3, by temperaturecontrol means (not shown).

In the excitation chamber 16, the NH₃ gas is ionized to generate an NH₃gas plasma 23. The excited ammonia of the NH₃ gas plasma 23 in theexcitation chamber 16 is fed to the precursor (M_(x)Cl_(y)) 22 insidethe chamber 1 through the opening portion 14. As a result, the metalcomponent of the precursor (M_(x)Cl_(y)) 22 and ammonia react to form ametal nitride (MN). At this time, the excitation chamber 16 ismaintained by the plasma at a predetermined temperature (e.g., 200 to400° C.) which is higher than the temperature of the substrate 3.

The metal nitride (MN) formed within the chamber 1 is transported towardthe substrate 3 controlled to a low temperature, whereby a thin MN film24 is formed on the surface of the substrate 3. After the thin MN film24 is formed, the supply of the NH₃ gas and the supply of power to thepower source 19 are cut off. Thus, the precursor (M_(x)Cl_(y)) 22 istransported toward the substrate 3 controlled to a lower temperaturethan the temperature of the metal member 7. The precursor (M_(x)Cl_(y))22 transported toward the substrate 3 is converted into only metal (M)ions by a reduction reaction, and directed at the substrate 3 to form athin M film 25 on the thin MN film 24 placed on the substrate 3. Abarrier metal film 26 is composed of the thin MN film 24 and the thin Mfilm 25 (see FIG. 2). The gases and the etching products that have notbeen involved in the reactions are exhausted through an exhaust port 27.

With the above-described barrier metal film production apparatus,similar to the first embodiment to the third embodiment, the metal isformed by plasmas to produce the barrier metal film 26. Thus, thebarrier metal film 26 can be formed uniformly to a small thickness.Consequently, the barrier metal film 26 can be formed highly accuratelyat a high speed with excellent burial properties in a very smallthickness even to the interior of a tiny depression, for example severalhundred nanometers wide, which has been provided in the substrate 3.

Furthermore, the metal member 7 itself is applied as an electrode forplasma generation. Thus, the plasma antenna 9 need not be providedaround the cylindrical portion of the chamber 1, and the degree offreedom of the construction in the surroundings can be increased.

A barrier metal film production apparatus and a barrier metal filmproduction method according to the fifth embodiment of the presentinvention will be described with reference to FIG. 8. FIG. 8 is aschematic side view of the barrier metal film production apparatusaccording to the fifth embodiment of the present invention. The samemembers as the members illustrated in FIG. 1 are assigned the samenumerals, and duplicate explanations are omitted.

Compared with the first embodiment shown in FIG. 1, the barrier metalfilm production apparatus shown in FIG. 8 lacks the opening portion 14,passage 15, excitation chamber 16, plasma antenna 17, matchinginstrument 18, power source 19 and flow controller 20. Nozzles 12 forsupplying a gas mixture of a source gas (Cl₂ gas) and a nitrogen gas (N₂gas) as a nitrogen-containing gas to the interior of the chamber 1 areconnected to the cylindrical portion of the chamber 1. The Cl₂ gas andthe N₂ gas are mixed in a mixed gas flow controller 81, and the gasmixture of the Cl₂ gas and the N₂ gas is supplied to the nozzle 12 viathe mixed gas flow controller 81. Other constructions are the same as inthe first embodiment.

With the above-described barrier metal film production apparatus, themixed gas comprising the Cl₂ gas and the N₂ gas is supplied through thenozzles 12 to the interior of the chamber 1, and electromagnetic wavesare shot from the plasma antenna 9 into the chamber 1. As a result, theCl₂ gas and the N₂ gas are ionized to generate a Cl₂ gas/N₂ gas plasma82. The Cl₂ gas/N₂ gas plasma 82 causes an etching reaction to the metalmember 7, forming a precursor (M_(x)Cl_(y): M is a metal such as W, Ti,Ta or TiSi) 22. Also, the precursor 22 and N₂ react to form a metalnitride (MN). At this time, the metal member 7 is maintained by theplasma (or temperature control means (not shown)) at a predeterminedtemperature (e.g., 200 to 400° C.) which is higher than the temperatureof the substrate 3.

The metal nitride (MN) formed within the chamber 1 is transported towardthe substrate 3 controlled to a low temperature, whereby a thin MN film24 is formed on the surface of the substrate 3. After the thin MN film24 is formed, the supply of the N₂ gas to the mixed gas flow controller81 is cut off. Thus, the precursor (M_(x)Cl_(y)) 22 is transportedtoward the substrate 3 controlled to a lower temperature than thetemperature of the metal member 7. The precursor (M_(x)Cl_(y)) 22transported toward the substrate 3 is converted into only metal (M) ionsby a reduction reaction, and directed at the substrate 3 to form a thinM film 25 on the surface of the substrate 3. A barrier metal film 26 iscomposed of the thin MN film 24 and the thin M film 25 (see FIG. 2).

The substrate 3, on which the barrier metal film 26 has been formed, isto have a thin copper (Cu) film or a thin aluminum (Al) film formed onthe barrier metal film 26 by a film forming device. Because of thepresence of the barrier metal film 26, there arise advantages, forexample, such that the thin MN film 24 eliminates diffusion of Cu intothe substrate 3, and the thin M film 25 ensures adhesion of Cu.

If the material to be formed as a film is a material unproblematic interms of adhesion (e.g., Al), or if it is a metal to which the nitridecan retain adhesion, the thin M film 25 can be omitted from the barriermetal film 26.

With the above-described barrier metal film production apparatus, thesame effects as in the first embodiment are obtained. In addition, thesupply line for the gases can be simplified, and the number of theplasma sources can be decreased. Thus, the cost of the product can bereduced.

The sixth embodiment of a barrier metal film production apparatus and abarrier metal film production method according to the present inventionwill be described with reference to FIG. 9. FIG. 9 is a schematic sideview of the barrier metal film production apparatus according to thesixth embodiment of the present invention. The same members as in thesecond and fifth embodiments illustrated in FIGS. 3 to 5 and 8 areassigned the same numerals, and duplicate explanations are omitted.

Compared with the second embodiment shown in FIG. 3, the barrier metalfilm production apparatus shown in FIG. 9 lacks the opening portion 14,passage 15, excitation chamber 16, plasma antenna 17, matchinginstrument 18, power source 19 and flow controller 20. Nozzles 12 forsupplying a gas mixture of a source gas (Cl₂ gas) and a nitrogen gas (N₂gas) as a nitrogen-containing gas to the interior of the chamber 1 areconnected to the cylindrical portion of the chamber 1. The Cl₂ gas andthe N₂ gas are mixed in a mixed gas flow controller 81, and the gasmixture of the Cl₂ gas and the N₂ gas is supplied to the nozzle 12 viathe mixed gas flow controller 81. Other constructions are the same as inthe second embodiment.

With the above-described barrier metal film production apparatus, themixed gas comprising the Cl₂ gas and the N₂ gas is supplied through thenozzles 12 to the interior of the chamber 1, and electromagnetic wavesare shot from the plasma antenna 34 into the chamber 1. As a result, theCl₂ gas and the N₂ gas are ionized to generate a Cl₂ gas/N₂ gas plasma82. The etched member 31, an electric conductor, is present below theplasma antenna 34. As stated earlier, however, the Cl₂ gas/N₂ gas plasma82 occurs stably between the etched member 31 and the substrate 3,namely, below the etched member 31.

The Cl₂ gas/N₂ gas plasma 82 causes an etching reaction to the etchedmember 31, forming a precursor (M_(x)Cl_(y): M is a metal such as W, Ti,Ta or TiSi) 22. Also, the precursor 22 and N₂ react to form a metalnitride (MN). At this time, the etched member 31 is maintained by theplasma (or temperature control means (not shown)) at a predeterminedtemperature (e.g., 200 to 400° C.) which is higher than the temperatureof the substrate 3.

The metal nitride (MN) formed within the chamber 1 is transported towardthe substrate 3 controlled to a low temperature, whereby a thin MN film24 is formed on the surface of the substrate 3. After the thin MN film24 is formed, the supply of the N₂ gas to the mixed gas flow controller81 is cut off. Thus, the precursor (M_(x)Cl_(y)) 22 is transportedtoward the substrate 3 controlled to a lower temperature than thetemperature of the etched member 31. The precursor (M_(x)Cl_(y)) 22transported toward the substrate 3 is converted into only metal (M) ionsby a reduction reaction, and directed at the substrate 3 to form a thinM film 25 on the thin MN film 24 on the substrate 3. A barrier metalfilm 26 is composed of the thin MN film 24 and the thin M film 25 (seeFIG. 2).

The substrate 3, on which the barrier metal film 26 has been formed, isto have a thin copper (Cu) film or a thin aluminum (Al) film formed onthe barrier metal film 26 by a film forming device. Because of thepresence of the barrier metal film 26, there arise advantages, forexample, such that the thin MN film 24 eliminates diffusion of Cu intothe substrate 3, and the thin M film 25 ensures adhesion of Cu.

If the material to be formed as a film is a material unproblematic interms of adhesion (e.g., Al), or if it is a metal to which the nitridecan retain adhesion, the thin M film 25 can be omitted from the barriermetal film 26.

With the above-described barrier metal film production apparatus, thesame effects as in the second embodiment are obtained. In addition, thesupply line for the gases can be simplified, and the number of theplasma sources can be decreased. Thus, the cost of the product can bereduced.

The seventh embodiment of a barrier metal film production apparatus anda barrier metal film production method according to the presentinvention will be described with reference to FIG. 10. FIG. 10 is aschematic side view of the barrier metal film production apparatusaccording to the seventh embodiment of the present invention. The samemembers as in the third and fifth embodiments illustrated in FIGS. 6 and8 are assigned the same numerals, and duplicate explanations areomitted.

Compared with the third embodiment shown in FIG. 6, the barrier metalfilm production apparatus shown in FIG. 10 lacks the opening portion 14,passage 15, excitation chamber 16, plasma antenna 17, matchinginstrument 18, power source 19 and flow controller 20. A gas mixture ofa source gas (Cl₂ gas) and a nitrogen gas (N₂ gas) as anitrogen-containing gas is supplied from a mixed gas flow controller 81to a second excitation chamber 44. Other constructions are the same asin the third embodiment.

With the above-described barrier metal film production apparatus, themixed gas comprising the Cl₂ gas and the N₂ gas is supplied into asecond passage 43 via the mixed gas flow controller 81, and fed into thesecond excitation chamber 44. Electromagnetic waves are shot from asecond plasma antenna 45 into the second excitation chamber 44. As aresult, the Cl₂ gas and the N₂ gas are ionized to generate a Cl₂ gas/N₂gas plasma 82. Since a predetermined differential pressure has beenestablished between the pressure inside the chamber 1 and the pressureinside the second excitation chamber 44 by the vacuum device 8, theexcited chlorine and excited nitrogen of the Cl₂ gas/N₂ gas plasma 82 inthe second excitation chamber 44 are fed to the etched member 41 insidethe chamber 1 through the second opening portion 42. The excitedchlorine causes an etching reaction to the etched member 41, forming aprecursor (M_(x)Cl_(y)) 22 inside the chamber 1. Also, the precursor 22and the excited nitrogen react to form a metal nitride (MN). At thistime, the etched member 41 is maintained at a predetermined temperature(e.g., 200 to 400° C.), which is higher than the temperature of thesubstrate 3, by a heater 50 provided in a ceiling board 30.

The metal nitride (MN) formed within the chamber 1 is transported towardthe substrate 3 controlled to a low temperature, whereby a thin MN film24 is formed on the surface of the substrate 3. After the thin MN film24 is formed, the supply of the N₂ gas to the mixed gas flow controller81 is cut off. Thus, the precursor (M_(x)Cl_(y)) 22 is transportedtoward the substrate 3 controlled to a lower temperature than thetemperature of the etched member 41. The precursor (M_(x)Cl_(y)) 22transported toward the substrate 3 is converted into only metal (M) ionsby a reduction reaction, and directed at the substrate 3 to form a thinM film 25 on the thin MN film 24 on the substrate 3. A barrier metalfilm 26 is composed of the thin MN film 24 and the thin M film 25 (seeFIG. 2).

The substrate 3, on which the barrier metal film 26 has been formed, isto have a thin copper (Cu) film or a thin aluminum (Al) film formed onthe barrier metal film 26 by a film forming device. Because of thepresence of the barrier metal film 26, there arise advantages, forexample, such that the thin MN film 24 eliminates diffusion of Cu intothe substrate 3, and the thin M film 25 ensures adhesion of Cu.

If the material to be formed as a film is a material unproblematic interms of adhesion (e.g., Al), or if it is a metal to which the nitridecan retain adhesion, the thin M film 25 can be omitted from the barriermetal film 26.

With the above-described barrier metal film production apparatus, thesame effects as in the third embodiment are obtained. In addition, thesupply line for the gases can be simplified, and the number of theplasma sources can be decreased. Thus, the cost of the product can bereduced.

The eighth embodiment of a barrier metal film production apparatus and abarrier metal film production method according to the present inventionwill be described with reference to FIG. 11. FIG. 11 is a schematic sideview of the barrier metal film production apparatus according to theeighth embodiment of the present invention. The same members as in thefourth embodiment and the fifth embodiment illustrated in FIGS. 7 and 8are assigned the same numerals, and duplicate explanations are omitted.

Compared with the fourth embodiment shown in FIG. 7, the barrier metalfilm production apparatus shown in FIG. 11 lacks the opening portion 14,passage 15, excitation chamber 16, plasma antenna 17, matchinginstrument 18, power source 19 and flow controller 20. Nozzles 12 forsupplying a gas mixture of a source gas (Cl₂ gas) and a nitrogen gas (N₂gas) as a nitrogen-containing gas to the interior of the chamber 1 areconnected to the cylindrical portion of the chamber 1. The Cl₂ gas andthe N₂ gas are mixed in a mixed gas flow controller 81, and the gasmixture of the Cl₂ gas and the N₂ gas is supplied to the nozzle 12 viathe mixed gas flow controller 81. Other constructions are the same as inthe fourth embodiment.

With the above-described barrier metal film production apparatus, themixed gas comprising the Cl₂ gas and the N₂ gas is supplied through thenozzles 12 to the interior of the chamber 1, and electromagnetic wavesare shot from the metal member 7 into the chamber 1. As a result, theCl₂ gas and the N₂ gas are ionized to generate a Cl₂ gas/N₂ gas plasma82. The Cl₂ gas/N₂ gas plasma 82 causes an etching reaction to the metalmember 7, forming a precursor (M_(x)Cl_(y): M is a metal such as W, Ti,Ta or TiSi) 22. Also, the precursor 22 and N₂ react to form a metalnitride (MN). At this time, the metal member 7 is maintained by theplasma (or temperature control means (not shown)) at a predeterminedtemperature (e.g., 200 to 400° C.) which is higher than the temperatureof the substrate 3.

The metal nitride (MN) formed within the chamber 1 is transported towardthe substrate 3 controlled to a low temperature, whereby a thin MN film24 is formed on the surface of the substrate 3. After the thin MN film24 is formed, the supply of the N₂ gas to the mixed gas flow controller81 is cut off. Thus, the precursor (M_(x)Cl_(y)) 22 is transportedtoward the substrate 3 controlled to a lower temperature than thetemperature of the metal member 7. The precursor (M_(x)Cl_(y)) 22transported toward the substrate 3 is converted into only metal (M) ionsby a reduction reaction, and directed at the substrate 3 to form a thinM film 25 on the thin MN film 24 on the substrate 3. A barrier metalfilm 26 is composed of the thin MN film 24 and the thin M film 25 (seeFIG. 2).

The substrate 3, on which the barrier metal film 26 has been formed, isto have a thin copper (Cu) film or a thin aluminum (Al) film formed onthe barrier metal film 26 by a film forming device. Because of thepresence of the barrier metal film 26, there arise advantages, forexample, such that the thin MN film 24 eliminates diffusion of Cu intothe substrate 3, and the thin M film 25 ensures adhesion of Cu.

If the material to be formed as a film is a material unproblematic interms of adhesion (e.g., Al), or if it is a metal to which the nitridecan retain adhesion, the thin M film 25 can be omitted from the barriermetal film 26.

With the above-described barrier metal film production apparatus, thesame effects as in the fourth embodiment are obtained. In addition, thesupply line for the gases can be simplified, and the number of theplasma sources can be decreased. Thus, the cost of the product can bereduced.

In the foregoing fifth to eighth embodiments, the N₂ gas is mixed withthe Cl₂ gas in the mixed gas flow controller 81, and the gas mixture issupplied into the chamber 1. However, the N₂ gas and the Cl₂ gas can besupplied through separate nozzles. Also, ammonia can be applied as thenitrogen-containing gas.

The ninth embodiment of the barrier metal film production apparatus andbarrier metal film production method of the present invention will bedescribed with reference to FIGS. 12 and 18. FIG. 12 is a schematic sideview of the barrier metal film production apparatus according to theninth embodiment of the present invention. FIG. 13 shows the sectionalstatus of a substrate illustrating a barrier metal film. FIGS. 14 and 15show the concept status of a barrier metal film in denitrification. FIG.16 shows the concept status of a barrier metal film in oxide layerformation. FIG. 17 represents the relationship between the contact angleof copper particles and the oxygen concentration of the substrate. FIG.18 shows the concept status of a barrier metal film in hydroxyl groupformation. FIG. 19 schematically shows a construction illustratinganother example of diluent gas supply means.

As shown in FIG. 12, a support platform 102 is provided near the bottomof a cylindrical chamber 101 made of, say, a ceramic (an insulatingmaterial), and a substrate 103 is placed on the support platform 102.Temperature control means 106, as control means, equipped with a heater104 and refrigerant flow-through means 105 is provided in the supportplatform 102 so that the support platform 102 is controlled to apredetermined temperature (for example, a temperature at which thesubstrate 103 is maintained at 100 to 200° C.) by the temperaturecontrol means 106.

An upper surface of the chamber 101 is an opening, which is closed witha metal member 107, as an etched member, made of a metal (e.g., W, Ti,Ta, or TiSi). The interior of the chamber 101 closed with the metalmember 107 is maintained at a predetermined pressure by a vacuum device108. A plasma antenna 109, as a coiled winding antenna of plasmageneration means, is provided around a cylindrical portion of thechamber 101. A matching instrument 110 and a power source 111 areconnected to the plasma antenna 109 to supply power.

A nozzle 112, as source gas supply means, for supplying a source gas (aCl₂ gas diluted with He or Ar to a chlorine concentration of ≦50%,preferably about 10%), containing chlorine as a halogen, to the interiorof the chamber 101 is connected to the cylindrical portion of thechamber 101 below the metal member 107. The nozzle 112 is fed with thesource gas via a flow controller 113. The source gas is supplied fromthe nozzle 112, and electromagnetic waves are shot from the plasmaantenna 109 into the chamber 101, whereby the Cl₂ gas is ionized togenerate a Cl₂ gas plasma (plasma generation means). Fluorine (F),bromine (Br) or iodine (I) can also be applied as the halogen to beincorporated into the source gas.

A nozzle 114, as nitrogen-containing gas supply means, for supplying anammonia gas (NH₃ gas) as a nitrogen-containing gas, to the interior ofthe chamber 101 is connected to the cylindrical portion of the chamber101 below the metal member 107. The NH₃ gas is supplied from the nozzle114, and electromagnetic waves are shot from the plasma antenna 109 intothe chamber 101, whereby the NH₃ gas is ionized to generate an NH₃ gasplasma (plasma generation means).

A diluent gas nozzle 121 is provided, as diluent gas supply means, forsupplying an Ar gas as a diluent gas, to the interior of the chamber 101above the surface of the substrate 103. The Ar gas is supplied from thediluent gas nozzle 121, and electromagnetic waves are shot from theplasma antenna 109 into the chamber 101, whereby the Ar gas is ionizedto generate an Ar gas plasma (surface treatment plasma generationmeans).

As described above, the diluent gas supply means applies the Ar gas asthe diluent gas for the Cl₂ gas. In this case, as shown in FIG. 19, acontrol valve 122 may be provided at the site of merger between thesource gas (Cl₂ gas) and the diluent gas (Ar gas) so that the Cl₂ gas isstopped during generation of the Ar gas plasma, and only the Ar gas issupplied through the nozzle 112. According to this construction, thereis no need for the provision of the diluent gas nozzle 121, presentingadvantage in space.

An oxygen gas nozzle 115 is provided, as oxygen gas supply means, forsupplying an oxygen gas (O₂ gas) to the interior of the chamber 101above the surface of the substrate 103. The O₂ gas is supplied from theoxygen gas nozzle 115, and electromagnetic waves are shot from theplasma antenna 109 into the chamber 101, whereby the O₂ gas is ionizedto generate an O₂ gas plasma (oxygen plasma generation means).

Furthermore, a hydrogen gas nozzle 116 is provided, as hydrogen gassupply means, for supplying a hydrogen gas (H₂ gas) to the interior ofthe chamber 101 above the surface of the substrate 103. The H₂ gas issupplied from the hydrogen gas nozzle 116, and electromagnetic waves areshot from the plasma antenna 109 into the chamber 101, whereby the H₂gas is ionized to generate an H₂ gas plasma (hydroxyl group plasmageneration means).

With the above-described barrier metal film production apparatus, thesource gas is supplied through the nozzle 112 to the interior of thechamber 101, and electromagnetic waves are shot from the plasma antenna109 into the chamber 101. As a result, the Cl₂ gas is ionized togenerate a Cl₂ gas plasma (source gas plasma). The Cl₂ gas plasma causesan etching reaction to the metal member 107, forming a precursor(M_(x)Cl_(y): M is a metal such as W, Ti, Ta or TiSi) 120. The metalmember 107 is maintained by the plasma at a predetermined temperature(e.g., 200 to 400° C.) which is higher than the temperature of thesubstrate 103.

Also, the NH₃ gas is supplied into the chamber 101 through the nozzle114, and electromagnetic waves are shot from the plasma antenna 109 intothe chamber 101. Thus, the NH₃ gas is ionized to generate an NH₃ gasplasma, which causes a reduction reaction with the precursor 120,forming a metal nitride (MN). The metal nitride (MN) formed within thechamber 101 is transported toward the substrate 103 controlled to a lowtemperature, whereupon MN is formed into a film on the surface of thesubstrate 103 to produce a barrier metal film 123 (see FIG. 13).

The reaction for formation of the barrier metal film 123 can beexpressed by:

2MCl+2NH₃→2MN↓+HCl↑+2H₂↑

The gases and the etching products that have not been involved in thereaction are exhausted through an exhaust port 117.

After the barrier metal film 1123 has been formed, the Ar gas issupplied from the diluent gas nozzle 121, and electromagnetic waves areshot from the plasma antenna 109 into the chamber 101, therebygenerating an Ar gas plasma. On the surface of the substrate 103, thebarrier metal film 123 of MN has been formed, as shown in FIG. 14. Thus,upon generation of the Ar gas plasma, Ar⁺ etches the barrier metal film123 on the surface of the substrate 103, thereby performing a treatmentfor removing the nitrogen atoms (N) of the MN in the superficial layerto decrease the nitrogen content of the superficial layer relative tothe interior of the matrix of the barrier metal film 123(denitrification).

As shown in FIG. 14, the barrier metal film 123 comprises M and N in anamorphous state. In this state, N of a lower mass is preferentiallyremoved by Ar⁺, so that the superficial layer of the barrier metal film123 (for example, up to a half, preferably about a third, of the entirefilm thickness) is denitrified. As a result, there emerges the barriermetal film 123 of a two-layer structure, a metal layer 123 asubstantially composed of M, and an MN layer 123 b, as shown in FIG. 15.On this occasion, the entire film thickness of the barrier metal film123 remains the film thickness having the single layer.

Immediately before formation of the most superficial layer of thebarrier metal film 123 is completed, a trace amount of O₂ gas issupplied through the oxygen gas nozzle 115 into the chamber 101. At thesame time, electromagnetic waves are shot from the plasma antenna 109into the chamber 101 to generate an O₂ gas plasma. As a result, an oxidelayer 124 is formed on the surface of the metal layer 123 a composedsubstantially of M, as shown in FIG. 16. Since the oxide layer 124 hasbeen formed, if a metal (e.g., copper) is deposited (formed as a film)on the surface of the barrier metal film 123, wetting with the metal issatisfactory, thus increasing adhesion.

In detail, it has been confirmed, as shown in FIG. 17, that the higherthe oxygen concentration of the substrate 103, the smaller the contactangle θ of a copper particle (the angle that takes minimal surfaceenergy in the presence of a balanced surface tension when the substrateis considered to be a solid and copper is deemed to be a liquid). Thatis, as the oxygen concentration of the substrate 103 increases, thecopper particle adheres in a collapsed state (a state of high wetting)to the surface of the substrate 103. Hence, the O₂ gas plasma isgenerated to form the oxide layer 124 on the surface of the metal layer123 a. By so doing, the oxygen concentration of the substrate 103 can beincreased, leading to satisfactory wetting with the metal (copper) to beformed as a film.

After formation of the oxide layer 124 on the surface of the metal layer123 a, the H₂ gas is supplied from the hydrogen gas nozzle 116 into thechamber 101, and electromagnetic waves are shot from the plasma antenna109 into the chamber 101, thereby generating an H₂ gas plasma. As aresult, hydroxyl groups (OH groups) are formed on the surface of theoxide layer 124, as shown in FIG. 18. These hydroxyl groups increasehydrophilicity, and can further enhance the adhesion of the metal(copper) to be formed as a film.

With the above-described barrier metal film production apparatus, themetal is formed by the plasma to produce the barrier metal film 123.Thus, the barrier metal film 123 can be formed uniformly to a smallthickness. Consequently, the barrier metal film 123 can be formed highlyaccurately at a high speed with excellent burial properties in a verysmall thickness even to the interior of a tiny depression, for exampleseveral hundred nanometers wide, which has been provided in thesubstrate 103.

Moreover, denitrification of the barrier metal film 123 is carried outby removing the nitrogen atoms with the Ar gas plasma. Thus, the barriermetal film 123 can be granted the two-layer structure, the metal layer123 a substantially composed of M, and the MN layer 123 b. In addition,the entire film thickness can remain the film thickness constructed fromthe single layer. Thus, the barrier metal film 123 can be formed in atwo-layer structure without being thickened. Of the two layers, themetal layer 123 a can retain adhesion to a metal to be formed as a filmon the surface thereof, while the MN layer (123 b) can prevent diffusionof the metal. Hence, it becomes possible to produce the barrier metalfilm which can be formed with good adhesion to the metal to be formed asa film, with diffusion of the metal being eliminated.

Besides, the O₂ gas plasma is generated to form the oxide layer 124 onthe surface of the metal layer 123 a. Thus, when a metal is formed as afilm on the surface of the barrier metal film 123, wetting with themetal is satisfactory, and adhesion of the metal can be increased.Additionally, the H₂ gas plasma is generated to form hydroxyl groups (OHgroups) on the surface of the oxide layer 124. Thus, the hydrophilicityimproves, and can further increase the adhesion of the metal to beformed as a film.

It is permissible to omit the step of generating the H₂ gas plasma toform hydroxyl groups (OH groups) on the surface of the oxide layer 124.It is also allowable to omit the step of generating the O₂ gas plasma toform the oxide layer 124 on the surface of the metal layer 123 a.

The barrier metal film production apparatus and barrier metal filmproduction method according to the tenth embodiment of the presentinvention will be described with reference to FIG. 20. FIG. 20schematically shows the construction of the barrier metal filmproduction apparatus according to the tenth embodiment of the presentinvention. The same members as the members shown in FIG. 12 are assignedthe same numerals, and duplicate explanations are omitted. FIG. 21 showsthe concept status of an example of production of a barrier metal filmby the barrier metal film production apparatus according to the tenthembodiment of the present invention.

Compared with the barrier metal film production apparatus of the ninthembodiment shown in FIG. 12, the barrier metal film production apparatusof the tenth embodiment shown in FIG. 20 lacks the diluent gas nozzle121. In the ninth embodiment, the Ar gas is supplied from the diluentgas nozzle 121 to generate an Ar gas plasma. Using the Ar gas plasma,Ar⁺ etches the barrier metal film 123 on the surface of the substrate103, thereby performing a treatment for removing the nitrogen atoms (N)of the MN in the superficial layer to decrease the nitrogen content ofthe superficial layer relative to the interior of the matrix of thebarrier metal film 123 (denitrification). In the present tenthembodiment, on the other hand, when denitrification is to be performed,the O₂ gas is supplied from the oxygen gas nozzle 115 to generate an O₂gas plasma. O₂ ⁺ etches the barrier metal film 123 on the surface of thesubstrate 103, performing denitrification. After denitrification, theamount of the O₂ gas is decreased to form the oxide layer 124 (see FIG.16). Other constructions and actions are the same as in the ninthembodiment.

The tenth embodiment can decrease the number of the nozzles forsupplying the gases, thus bringing advantage in space.

In the barrier metal film production apparatus of the tenth embodiment,the O₂ gas plasma can be used only for the formation of the oxide layer124 (see FIG. 16) without being used for etching. In this case, thebarrier metal film 123 is only the single layer, MN layer 123 b. If themetal to be formed as a film over the substrate 103 is a metalunproblematic in terms of adhesion (such as Al), for example, thetreatment for forming the metal layer 123 a by etching can be omitted.

In the barrier metal film production apparatus of the tenth embodiment,moreover, the O₂ gas plasma can be used similarly only for the formationof the oxide layer 124 (see FIG. 16) without being used for etching. Inthis case, however, after the MN layer 123 b is formed, the supply ofthe NH₃ gas from the nozzle 114 is cut off to terminate the reaction ofthe precursor 120 with an NH₃ gas plasma. Then, as shown in FIG. 21, themetal component of the precursor 120 is superposed on the MN layer 123b, whereby the metal layer 123 a can be formed.

The reaction for formation of the metal layer 123 a from the metalcomponent of the precursor 120 can be expressed by:

2MCl→2M↓+Cl₂↑

The barrier metal film production apparatus and barrier metal filmproduction method according to the eleventh embodiment of the presentinvention will be described with reference to FIG. 22. FIG. 22schematically shows the construction of the barrier metal filmproduction apparatus according to the eleventh embodiment of the presentinvention. The same members as in the barrier metal film productionapparatus shown in FIG. 12 are assigned the same numerals, and duplicateexplanations are omitted.

As shown in FIG. 22, a support platform 102 is provided near the bottomof a chamber 101, and a substrate 103 is placed on the support platform102. Temperature control means 106, as control means, equipped with aheater 104 and refrigerant flow-through means 105 is provided in thesupport platform 102 so that the support platform 102 is controlled to apredetermined temperature (for example, a temperature at which thesubstrate 103 is maintained at 100 to 200° C.) by the temperaturecontrol means 106. An upper surface of the chamber 101 is an opening,which is closed with a metal member 107 (e.g., W, Ti, Ta, or TiSi). Theinterior of the chamber 101 closed with the metal member 107 ismaintained at a predetermined pressure by a vacuum device 108. A plasmaantenna 109 is provided around a cylindrical portion of the chamber 101.A matching instrument 110 and a power source 111 are connected to theplasma antenna 109 to supply power.

A nozzle 112 for supplying a source gas is connected to the cylindricalportion of the chamber 101 below the metal member 107. The source gas issupplied from the nozzle 112, and electromagnetic waves are shot fromthe plasma antenna 109 into the chamber 101, whereby the Cl₂ gas isionized to generate a Cl₂ gas plasma (plasma generation means).

A diluent gas nozzle 121 is provided for supplying an Ar gas to theinterior of the chamber 101. Also, electromagnetic waves are shot fromthe plasma antenna 109 into the chamber 101. Thus, the Ar gas is ionizedto generate an Ar gas plasma (surface treatment plasma generationmeans). If an Ar gas is applied as the diluent gas for the Cl₂ gas,diluent gas supply means may be constructed, similar to the ninthembodiment, such that only the Ar gas is supplied from the nozzle 112.

An oxygen gas nozzle 115 is provided for supplying an oxygen gas (O₂gas) to the interior of the chamber 101. Also, electromagnetic waves areshot from the plasma antenna 109 into the chamber 101. Thus, the O₂ gasis ionized to generate an O₂ gas plasma (oxygen plasma generationmeans). Moreover, a hydrogen gas nozzle 116 is provided for supplying ahydrogen gas (H₂ gas) to the interior of the chamber 101. Also,electromagnetic waves are shot from the plasma antenna 109 into thechamber 101. Thus, the H₂ gas is ionized to generate an H₂ gas plasma(hydroxyl group plasma generation means).

Slit-shaped opening portions 131 are formed at a plurality of locations(for example, four locations; only one of the locations is shown in thedrawing) in the periphery of a lower part of the cylindrical portion ofthe chamber 101, and one end of a tubular passage 132 is fixed to theopening portion 131. A tubular excitation chamber 33 made of aninsulator is provided halfway through the passage 132, and a coiledplasma antenna 134 is provided around the excitation chamber 133. Theplasma antenna 134 is connected to a matching instrument 135 and a powersource 136 to receive power. The plasma antenna 134, the matchinginstrument 135 and the power source 136 constitute excitation means. Aflow controller 137 is connected to the other end of the passage 132,and an ammonia gas (NH₃ gas) as a nitrogen-containing gas is suppliedinto the passage 132 via the flow controller 137.

Separately, the NH₃ gas is supplied into the passage 132 via the flowcontroller 137 and fed into the excitation chamber 133. By shootingelectromagnetic waves from the plasma antenna 134 into the excitationchamber 133, the NH₃ gas is ionized to generate an NH₃ gas plasma 138.Since a predetermined differential pressure has been established betweenthe pressure inside the chamber 101 and the pressure inside theexcitation chamber 133 by the vacuum device 108, the excited ammonia ofthe NH₃ gas plasma 138 in the excitation chamber 133 is fed to theprecursor (M_(x)Cl_(y)) 120 inside the chamber 101 through the openingportion 131.

That is, excitation means for exciting the nitrogen-containing gas inthe excitation chamber 133 isolated from the chamber 101 is constructed.Because of this construction, the metal component of the precursor(M_(x)Cl_(y)) 120 and ammonia react to form a metal nitride (MN)(formation means). At this time, the metal member 107 and the excitationchamber 133 are maintained by the plasmas at predetermined temperatures(e.g., 200 to 400° C.) which are higher than the temperature of thesubstrate 103.

With the above-described barrier metal film production apparatus, thesource gas is supplied through the nozzle 112 to the interior of thechamber 101, and electromagnetic waves are shot from the plasma antenna109 into the chamber 101. As a result, a Cl₂ gas plasma (source gasplasma) occurs. The Cl₂ gas plasma causes an etching reaction to themetal member 107, forming a precursor (M_(x)Cl_(y)) 120. The metalmember 107 is maintained by the plasma at a predetermined temperature(e.g., 200 to 400° C.) which is higher than the temperature of thesubstrate 103.

The excited ammonia of the NH₃ gas plasma 138 in the excitation chamber133 is fed to the precursor (M_(x)Cl_(y)) 120 inside the chamber 101through the opening portion 131. Thus, a metal nitride (MN) is formedinside the chamber 101. The resulting metal nitride (MN) is transportedtoward the substrate 103 controlled to a low temperature, whereby abarrier metal film 23 is formed on the surface of the substrate 103. Thegases and the etching products, which have not been involved in thereaction, are exhausted through an exhaust port 117.

After the barrier metal film 123 is formed, the Ar gas is supplied fromthe diluent gas nozzle 121, and electromagnetic waves are shot from theplasma antenna 109 into the chamber 101 to generate an Ar gas plasma.Using the Ar gas plasma, Ar⁺ etches the barrier metal film 123 on thesurface of the substrate 103, thereby performing a treatment forremoving the nitrogen atoms (N) of the MN in the superficial layer todecrease the nitrogen content of the superficial layer relative to theinterior of the matrix of the barrier metal film 123 (denitrification).As a result, there emerges the barrier metal film 123 of a two-layerstructure, a metal layer 123 a substantially composed of M, and an MNlayer 123 b (see FIG. 15).

Immediately before formation of the most superficial layer of thebarrier metal film 123 is completed, a trace amount of O₂ gas issupplied through the oxygen gas nozzle 115 into the chamber 101. At thesame time, electromagnetic waves are shot from the plasma antenna 109into the chamber 101 to generate an O₂ gas plasma. As a result, an oxidelayer 124 is formed on the surface of the metal layer 123 a composedsubstantially of M (see FIG. 16). Since the oxide layer 124 has beenformed, if a metal (e.g., copper) is deposited (formed as a film) on thesurface of the barrier metal film 123, wetting with the metal issatisfactory, thus increasing adhesion.

After formation of the oxide layer 124 on the surface of the metal layer123 a, the H₂ gas is supplied from the hydrogen gas nozzle 116 into thechamber 101, and electromagnetic waves are shot from the plasma antenna109 into the chamber 101, thereby generating an H₂ gas plasma. As aresult, hydroxyl groups (OH groups) are formed on the surface of theoxide layer 124 (see FIG. 18). These hydroxyl groups increasehydrophilicity, and can further enhance the adhesion of the metal(copper) to be formed as a film.

With the above-described barrier metal film production apparatus, thebarrier metal film 123 can be formed at a high speed with excellentburial properties in a very small thickness, as in the ninth embodiment.In addition, the entire film thickness can remain the film thicknessconstructed from the single layer. In this state, it becomes possible toproduce the barrier metal film which can be formed with good adhesion tothe metal to be formed as a film, with diffusion of the metal beingeliminated.

Besides, when a metal is formed as a film on the surface of the barriermetal film 123, wetting with the metal is satisfactory, and adhesion ofthe metal can be increased. Additionally, the hydrophilicity improves,and can further increase the adhesion of the metal to be formed as afilm.

Further, the NH₃ gas plasma 138 is generated in the excitation chamber133 isolated from the chamber 101. Thus, the influence of the NH₃ gasplasma 138 is not exerted on the surface of the substrate 103.

It is permissible to omit the step of generating the H₂ gas plasma toform hydroxyl groups (OH groups) on the surface of the oxide layer 124.It is also allowable to omit the step of generating the O₂ gas plasma toform the oxide layer 124 on the surface of the metal layer 123 a.

The barrier metal film production apparatus according to the eleventhembodiment shown in FIG. 22 may have a construction in which the diluentgas nozzle 121 is not provided. In the eleventh embodiment, the Ar gasis supplied from the diluent gas nozzle 121 to generate an Ar gasplasma. Ar⁺ etches the barrier metal film 123 on the surface of thesubstrate 103, thereby removing the nitrogen atoms (N) of the MN in thesuperficial layer to decrease the nitrogen content of the superficiallayer relative to the interior of the matrix of the barrier metal film123 (denitrification). When denitrification is to be performed, the O₂gas is supplied from the oxygen gas nozzle 115 to generate an O₂ gasplasma, and O₂ ⁺ etches the barrier metal film 123 on the surface of thesubstrate 103, thereby carrying out denitrification. Afterdenitrification, the amount of the O₂ gas is decreased to form the oxidelayer 124 (see FIG. 16).

In this case, the number of the nozzles for supplying the gases can bedecreased, thus bringing advantage in space.

The O₂ gas plasma can be used only for the formation of the oxide layer124 (see FIG. 16) without being used for etching. In this case, thebarrier metal film 123 is only the single layer, MN layer 123 b. If themetal to be formed as a film over the substrate 103 is a metalunproblematic in terms of adhesion (such as Al), for example, thetreatment for forming the metal layer 123 a by etching can be omitted.

Moreover, the O₂ gas plasma can be used similarly only for the formationof the oxide layer 124 (see FIG. 16) without being used for etching.After the MN layer 123 b is formed, the supply of the NH₃ gas and thesupply of power to the power source 136 may be cut off. As a result, theprecursor (M_(x)Cl_(y)) 120 is transported toward the substrate 103controlled to a lower temperature than the temperature of the metalmember 107. The precursor (M_(x)Cl_(y)) 120 transported toward thesubstrate 103 is converted into only metal (M) ions by a reductionreaction, and directed at the substrate 3. Thus, the metal layer 123 ais superposed on the MN layer 123 b of the substrate 103. In thismanner, the metal layer 123 a can be formed (see FIG. 21).

A barrier metal film production apparatus and a barrier metal filmproduction method according to a twelfth embodiment of the presentinvention will be described with reference to FIGS. 23 to 25. FIG. 23 isa schematic side view of the barrier metal film production apparatusaccording to the twelfth embodiment of the present invention. FIG. 24 isa view taken along the arrowed line XIII-XIII of FIG. 23. FIG. 25 is aview taken along the arrowed line XIV-XIV of FIG. 24. The same membersas the members illustrated in FIGS. 12 to 22 are assigned the samenumerals, and duplicate explanations are omitted.

An upper surface of the chamber 101 is an opening, which is closed witha disk-shaped ceiling board 141 made of an insulating material (forexample, a ceramic). An etched member 142 made of a metal (e.g., W, Ti,Ta or TiSi) is interposed between the opening at the upper surface ofthe chamber 101 and the ceiling board 141. The etched member 142 isprovided with a ring portion 143 fitted to the opening at the uppersurface of the chamber 101. A plurality of (12 in the illustratedembodiment) protrusions 144, which extend close to the center in thediametrical direction of the chamber 101 and have the same width, areprovided in the circumferential direction on the inner periphery of thering portion 143.

The protrusions 144 are integrally or removably attached to the ringportion 143. Notches (spaces) 145 formed between the protrusions 144 arepresent between the ceiling board 141 and the interior of the chamber101. The ring portion 143 is earthed, and the plural protrusions 144 areelectrically connected together and maintained at the same potential.Temperature control means (not shown), such as a heater, is provided inthe etched member 142 to control the temperature of the etched member142 to 200 to 400° C., for example.

Second protrusions shorter in the diametrical direction than theprotrusions 144 can be arranged between the protrusions 144. Moreover,short protrusions can be arranged between the protrusion 144 and thesecond protrusion. By so doing, the area of the etched member, an objectto be etched, can be secured, with an induced current being suppressed.

A planar winding-shaped plasma antenna 146, for converting theatmosphere inside the chamber 101 into a plasma, is provided above theceiling board 141. The plasma antenna 146 is formed in a planar ringshape parallel to the surface of the ceiling board 141. A matchinginstrument 110 and a power source 111 are connected to the plasmaantenna 146 to supply power. The etched member 142 has the plurality ofprotrusions 144 provided in the circumferential direction on the innerperiphery of the ring portion 143, and includes the notches (spaces) 145formed between the protrusions 144. Thus, the protrusions 144 arearranged between the substrate 103 and the ceiling board 141 in adiscontinuous state relative to the flowing direction of electricity inthe plasma antenna 146.

At a cylindrical portion of the chamber 101, there are provided a nozzle112 for supplying a source gas into the chamber 101, a nozzle 114 forsupplying an NH₃ gas into the chamber 101, a diluent gas nozzle 121 forsupplying an Ar gas into the chamber 101, an oxygen gas nozzle 115 forsupplying an O₂ gas into the chamber 101, and a hydrogen gas nozzle 116for supplying an H₂ gas into the chamber 101.

With the above-described barrier metal film production apparatus, thesource gas is supplied through the nozzles 112 to the interior of thechamber 101, and electromagnetic waves are shot from the plasma antenna146 into the chamber 101. As a result, the Cl₂ gas is ionized togenerate a Cl₂ gas plasma (source gas plasma). The etched member 142, anelectric conductor, is present below the plasma antenna 146. However,the Cl₂ gas plasma occurs stably between the etched member 142 and thesubstrate 103, namely, below the etched member 142, under the followingaction:

The action by which the Cl₂ gas plasma is generated below the etchedmember 142 will be described. As shown in FIG. 25, a flow A ofelectricity in the plasma antenna 146 of the planar ring shape crossesthe protrusions 144. At this time, an induced current B occurs on thesurface of the protrusion 144 opposed to the plasma antenna 146. Sincethe notches (spaces) 145 are present in the etched member 142, theinduced current B flows onto the lower surface of each protrusion 144,forming a flow a in the same direction as the flow A of electricity inthe plasma antenna 146 (Faraday shield).

When the etched member 142 is viewed from the substrate 103, therefore,there is no flow in a direction in which the flow A of electricity inthe plasma antenna 146 is canceled out. Furthermore, the ring portion143 is earthed, and the protrusions 144 are maintained at the samepotential. Thus, even though the etched member 142, an electricconductor, exists, the electromagnetic wave is reliably thrown from theplasma antenna 146 into the chamber 101. Consequently, the Cl₂ gasplasma is stably generated below the etched member 142.

The Cl₂ gas plasma causes an etching reaction to the etched member 142,forming a precursor (M_(x)Cl_(y): M is a metal such as W, Ti, Ta orTiSi) 120.

Separately, the NH₃ gas is supplied into the chamber 101 through thenozzle 114, and electromagnetic waves are shot from the plasma antenna146 into the chamber 110. Thus, the NH₃ gas is ionized to generate anNH₃ gas plasma, which causes a reduction reaction with the precursor120, forming a metal nitride (MN). The metal nitride (MN) formed withinthe chamber 101 is transported toward the substrate 103 controlled to alow temperature, whereupon MN is formed into a film on the surface ofthe substrate 103 to produce a barrier metal film 123 (see FIG. 13).

After the barrier metal film 123 has been formed, the Ar gas is suppliedfrom the diluent gas nozzle 121, and electromagnetic waves are shot fromthe plasma antenna 146 into the chamber 101, thereby generating an Argas plasma. Generation of the Ar gas plasma results in the etching ofthe barrier metal film 123 on the surface of the substrate 103, therebyperforming denitrification, a treatment for removing the nitrogen atoms(N) of the MN in the superficial layer of the barrier metal film 123 todecrease the nitrogen content of the superficial layer relative to theinterior of the matrix of the barrier metal film 123.

Immediately before formation of the most superficial layer of thebarrier metal film 123 is completed, a trace amount of O₂ gas issupplied through the oxygen gas nozzle 115 into the chamber 101. At thesame time, electromagnetic waves are shot from the plasma antenna 146into the chamber 101 to generate an O₂ gas plasma. As a result, an oxidelayer 124 (see FIG. 16) is formed on the surface of the metal layer 123a composed substantially of M (see FIG. 16). Since the oxide layer 124has been formed, if a metal (e.g., copper) is deposited (formed as afilm) on the surface of the barrier metal film 123, wetting with themetal is satisfactory, thus increasing adhesion.

After formation of the oxide layer 124 (see FIG. 16) on the surface ofthe metal layer 123 a (FIG. 16), the H₂ gas is supplied from thehydrogen gas nozzle 116 into the chamber 101, and electromagnetic wavesare shot from the plasma antenna 146 into the chamber 101, therebygenerating an H₂ gas plasma. As a result, hydroxyl groups (OH groups)are formed on the surface of the oxide layer 124 (see FIG. 18). Thesehydroxyl groups increase hydrophilicity, and can further enhance theadhesion of the metal (copper) to be formed as a film.

It is permissible to omit the step of generating the H₂ gas plasma toform hydroxyl groups (OH groups) on the surface of the oxide layer 124(see FIG. 18). It is also allowable to omit the step of generating theO₂ gas plasma to form the oxide layer 124 (FIG. 16) on the surface ofthe metal layer 123 a (FIG. 16). Furthermore, it is possible tosuperpose the metal layer 123 a, forming the barrier metal film 123. Itis also possible to form the barrier metal film 123 free from the metallayer 123 a.

Beside, the same nozzle construction as in the tenth embodiment (seeFIG. 20) omitting the diluent gas nozzle 121 may be adopted in aconfiguration for formation of the precursor 120 with the exception ofthe etched member 142 and the plasma antenna 146. Moreover, the sameconstruction as in the eleventh embodiment (see FIG. 22) having theexcitation chamber 133, etc. instead of the nozzle 114 may be adopted ina configuration excepting the etched member 142 and the plasma-antenna146.

With the above-described barrier metal film production apparatus, thebarrier metal film 123 can be formed uniformly to a small thickness.Consequently, the barrier metal film 123 can be formed highly accuratelyat a high speed with excellent burial properties in a very smallthickness even to the interior of a tiny depression, for example severalhundred nanometers wide, which has been provided in the substrate 103.

In addition, the etched member 142 has the plurality of protrusions 144provided in the circumferential direction on the inner periphery of thering portion 143, and includes the notches (spaces) 145 formed betweenthe protrusions 144. Thus, the induced currents generated in the etchedmember 142 flow in the same direction as the flowing direction ofelectricity in the plasma antenna 146, when viewed from the substrate103. Therefore, even though the etched member 142, an electricconductor, exists below the plasma antenna 146, the electromagneticwaves are reliably thrown from the plasma antenna 146 into the chamber101. Consequently, the Cl₂ gas plasma can be stably generated below theetched member 142.

A barrier metal film production apparatus and a barrier metal filmproduction method according to the thirteenth embodiment of the presentinvention will be described with reference to FIG. 26. FIG. 26 is aschematic side view of a barrier metal film production apparatusaccording to the third embodiment of the present invention. The samemembers as the members illustrated in FIGS. 12 to 25 are assigned thesame numerals, and duplicate explanations are omitted.

The opening of an upper portion of a chamber 101 is closed with aceiling board 141. An etched member 148 made of a metal (e.g., W, Ti, Taor TiSi) is provided on a lower surface of the ceiling board 141, andthe etched member 148 is of a quadrangular pyramidal shape. Slit-shapedopening portions 151 are formed at a plurality of locations (forexample, four locations; one of the locations is shown in the drawing)in the periphery of an upper part of the cylindrical portion of thechamber 101, and one end of a tubular passage 152 is fixed to theopening portion 151. A tubular excitation chamber 153 made of aninsulator is provided halfway through the passage 152, and a coiledplasma antenna 154 is provided around the excitation chamber 153. Theplasma antenna 154 is connected to a matching instrument 157 and a powersource 158 to receive power.

A flow controller 155 is connected to the other end of the passage 152,and a chlorine-containing source gas (a Cl₂ gas diluted with He or Ar toa chlorine concentration of ≦50%, preferably about 10%) is supplied intothe passage 152 via the flow controller 155. By shooting electromagneticwaves from the plasma antenna 154 into the excitation chamber 153, theCl₂ gas is ionized to generate a Cl₂ gas plasma (source gas plasma) 156.Because of the generation of the Cl₂ gas plasma 156, excited chlorine isfed into the chamber 101 through the opening portion 151, whereupon theetched member 148 is etched with excited chlorine.

At a cylindrical portion of the chamber 101, there are provided a nozzle114 for supplying an NH₃ gas into the chamber 101, a diluent gas nozzle121 for supplying an Ar gas into the chamber 101, an oxygen gas nozzle115 for supplying an O₂ gas into the chamber 101, and a hydrogen gasnozzle 116 for supplying an H₂ gas into the chamber 101. Around thechamber 101, a plasma antenna 109, a matching instrument 110 and a powersource 111 are provided to generate an NH₃ gas plasma, an Ar gas plasma,an O₂ gas plasma, and an H₂ gas plasma.

With the above-described barrier metal film production apparatus, thesource gas is supplied into the passage 152 via the flow controller 155and fed into the excitation chamber 153. By shooting electromagneticwaves from the plasma antenna 154 into the excitation chamber 153, theCl₂ gas is ionized to generate a Cl₂ gas plasma (source gas plasma) 156.Since a predetermined differential pressure has been established betweenthe pressure inside the chamber 101 and the pressure inside theexcitation chamber 153 by the vacuum device 108, the excited chlorine ofthe Cl₂ gas plasma 156 in the excitation chamber 153 is fed to theetched member 148 inside the chamber 101 through the opening portion151. The excited chlorine causes an etching reaction to the etchedmember 148, forming a precursor 120 inside the chamber 101. At thistime, the etched member 148 is maintained at a predetermined temperature(e.g., 200 to 400° C.), which is higher than the temperature of thesubstrate 103, by a heater 150 provided in the ceiling board 141.

Separately, the NH₃ gas is supplied into the chamber 101 through thenozzle 114, and electromagnetic waves were shot from the plasma antenna109 in to the chamber 110. Thus, the NH₃ gas is ionized to generate anNH₃ gas plasma, which causes a reduction reaction with the precursor120, forming a metal nitride (MN). The metal nitride (MN) formed withinthe chamber 101 is transported toward the substrate 103 controlled to alow temperature, whereupon MN is formed into a film on the surface ofthe substrate 103 to produce a barrier metal film 123 (see FIG. 13).

After the barrier metal film 123 has been formed, the Ar gas is suppliedfrom the diluent gas nozzle 121, and electromagnetic waves are shot fromthe plasma antenna 109 into the chamber 101, thereby generating an Argas plasma. Generation of the Ar gas plasma results in the etching ofthe barrier metal film 123 on the surface of the substrate 103, therebyperforming denitrification, a treatment for removing the nitrogen atoms(N) of the MN in the superficial layer of the barrier metal film 123 todecrease the nitrogen content of the superficial layer relative to theinterior of the matrix of the barrier metal film 123.

Immediately before formation of the most superficial layer of thebarrier metal film 123 is completed, a trace amount of O₂ gas issupplied through the oxygen gas nozzle 115 into the chamber 101. At thesame time, electromagnetic waves are shot from the plasma antenna 109into the chamber 101 to generate an O₂ gas plasma. As a result, an oxidelayer 124 (see FIG. 16) is formed on the surface of the metal layer 123a composed substantially of M (see FIG. 16). Since the oxide layer 124has been formed, if a metal (e.g., copper) is deposited (formed as afilm) on the surface of the barrier metal film 123, wetting with themetal is satisfactory, thus increasing adhesion.

After formation of the oxide layer 124 (see FIG. 16) on the surface ofthe metal layer 123 a (FIG. 16), the H₂ gas is supplied from thehydrogen gas nozzle 116 into the chamber 101, and electromagnetic wavesare shot from the plasma antenna 109 into the chamber 101, therebygenerating an H₂ gas plasma. As a result, hydroxyl groups (OH groups)are formed on the surface of the oxide layer 124 (see FIG. 18). Thesehydroxyl groups increase hydrophilicity, and can further enhance theadhesion of the metal (copper) to be formed as a film.

It is permissible to omit the step of generating the H₂ gas plasma toform hydroxyl groups (OH groups) on the surface of the oxide layer 124(see FIG. 18). It is also allowable to omit the step of generating theO₂ gas plasma to form the oxide layer 124 (FIG. 16) on the surface ofthe metal layer 123 a (FIG. 16). Furthermore, it is possible tosuperpose the metal layer 123 a, forming the barrier metal film 123. Itis also possible to form the barrier metal film 123 free from the metallayer 123 a.

Beside, the same nozzle construction as in the tenth embodiment (seeFIG. 20) omitting the diluent gas nozzle 121 may be adopted in aconfiguration for formation of the precursor 120 with the exception ofthe etched member 148, opening portion 151, passage 152, excitationchamber 153, plasma antenna 154, flow controller 155, matchinginstrument 157, and power source 158. Moreover, the same construction asin the eleventh embodiment (see FIG. 22) having the excitation chamber133, etc. instead of the nozzle 114 may be adopted in otherconfiguration for formation of the precursor 120.

With the above-described barrier metal film production apparatus, thebarrier metal film 123 can be formed uniformly to a small thickness.Consequently, the barrier metal film 123 can be formed highly accuratelyat a high speed with excellent burial properties in a very smallthickness even to the interior of a tiny depression, for example severalhundred nanometers wide, which has been provided in the substrate 103.

Furthermore, the Cl₂ gas plasma 156 is generated in the excitationchamber 153 isolated from the chamber 101. Thus, the substrate 103 isnot exposed to the Cl₂ gas plasma 156 any more, and the substrate 103becomes free from damage from the Cl₂ gas plasma 156.

As the means for generating the Cl₂ gas plasma 156 in the excitationchamber 153, namely, the means for exciting the source gas to convert itinto an excited source gas, it is possible to use microwaves, laser,electron rays, or synchrotron radiation. It is also permissible to formthe precursor by heating the metal filament to a high temperature. Theconstruction for isolating the Cl₂ gas plasma 156 from the substrate 103may be the provision of the excitation chamber 153 in the passage 152,or may be other construction, for example, the isolation of the chamber101.

A barrier metal film production apparatus and a barrier metal filmproduction method according to the fourteenth embodiment of the presentinvention will be described with reference to FIG. 27. FIG. 27 is aschematic side view of the barrier metal film production apparatusaccording to the fourteenth embodiment of the present invention. Thesame members as the members illustrated in FIGS. 12 to 26 are assignedthe same numerals, and duplicate explanations are omitted.

In the barrier metal film production apparatus according to thefourteenth embodiment, unlike the barrier metal film productionapparatus according to the ninth embodiment shown in FIG. 12, the plasmaantenna 9 is not provided around the cylindrical portion of the chamber101, but a metal member 107 is connected to a matching instrument 110and a power source 111 to receive power.

At the cylindrical portion of the chamber 101, there are provided anozzle 114 for supplying an NH₃ gas into the chamber 101, a diluent gasnozzle 121 for supplying an Ar gas into the chamber 101, an oxygen gasnozzle 115 for supplying an O₂ gas into the chamber 101, and a hydrogengas nozzle 116 for supplying an H₂ gas into the chamber 101. Bysupplying power to the metal member 107, an NH₃ gas plasma, an Ar gasplasma, an O₂ gas plasma, and an H₂ gas plasma are generated. Togenerate the NH₃ gas plasma, Ar gas plasma, O₂ gas plasma, and H₂ gasplasma, a coiled plasma antenna may be provided separately on thecylindrical portion of the chamber 101, and the plasma antenna may beconnected to a power source via a matching instrument.

With the above-described barrier metal film production apparatus, thesource gas is supplied from the nozzle 112 into the chamber 101, andelectromagnetic waves are shot from the metal member 107 into thechamber 101, whereby the Cl₂ gas is ionized to generate a Cl₂ gas plasma(source gas plasma). The Cl₂ gas plasma causes an etching reaction tothe metal member 107, producing a precursor (M_(x)Cl_(y)) 120. At thistime, the metal member 107 is maintained at a predetermined temperature(e.g., 200 to 400° C.), which is higher than the temperature of thesubstrate 103, by temperature control means (not shown).

Separately, the NH₃ gas is supplied into the chamber 101 through thenozzle 114, and electromagnetic waves are shot from the metal member 107into the chamber 101. Thus, the NH₃ gas is ionized to generate an NH₃gas plasma, which causes a reduction reaction with the precursor 120,forming a metal nitride (MN). The metal nitride (MN) formed within thechamber 101 is transported toward the substrate 103 controlled to a lowtemperature, whereupon MN is formed into a film on the surface of thesubstrate 103 to produce a barrier metal film 123 (see FIG. 13).

After the barrier metal film 123 has been formed, the Ar gas is suppliedfrom the diluent gas nozzle 121, and electromagnetic waves are shot fromthe metal member 107 into the chamber 101, thereby generating an Ar gasplasma. Generation of the Ar gas plasma results in the etching of thebarrier metal film 123 on the surface of the substrate 103, therebyperforming denitrification, a treatment for removing the nitrogen atoms(N) of the MN in the superficial layer of the barrier metal film 123 todecrease the nitrogen content of the superficial layer relative to theinterior of the matrix of the barrier metal film 123.

Immediately before formation of the most superficial layer of thebarrier metal film 123 is completed, a trace amount of O₂ gas issupplied through the oxygen gas nozzle 115 into the chamber 101. At thesame time, electromagnetic waves are shot from the metal member 107 intothe chamber 101 to generate an O₂ gas plasma. As a result, an oxidelayer 124 (see FIG. 16) is formed on the surface of a metal layer 123 acomposed substantially of M (see FIG. 16). Since the oxide layer 124 hasbeen formed, if a metal (e.g., copper) is deposited (formed as a film)on the surface of the barrier metal film 123, wetting with the metal issatisfactory, thus increasing adhesion.

After formation of the oxide layer 124 (see FIG. 16) on the surface ofthe metal layer 123 a (FIG. 16), the H₂ gas is supplied from thehydrogen gas nozzle 116 into the chamber 101, and electromagnetic wavesare shot from the metal member 107 into the chamber 101, therebygenerating an H₂ gas plasma. As a result, hydroxyl groups (OH groups)are formed on the surface of the oxide layer 124 (see FIG. 18). Thesehydroxyl groups increase hydrophilicity, and can further enhance theadhesion of the metal (copper) to be formed as a film.

It is permissible to omit the step of generating the H₂ gas plasma toform hydroxyl groups (OH groups) on the surface of the oxide layer 124(see FIG. 18). It is also allowable to omit the step of generating theO₂ gas plasma to form the oxide layer 124 (FIG. 16) on the surface ofthe metal layer 123 a (FIG. 16). Furthermore, it is possible tosuperpose the metal layer 123 a, forming the barrier metal film 123. Itis also possible to form the barrier metal film 123 free from the metallayer 123 a.

Beside, the same nozzle construction as in the tenth embodiment (seeFIG. 20) omitting the diluent gas nozzle 121 may be adopted in theconfiguration for formation of the precursor 120 with the exception ofthe metal member 107, matching instrument 110, and power source 111.Moreover, the same construction as in the eleventh embodiment (see FIG.22) having the excitation chamber 133, etc. instead of the nozzle 114may be adopted in other configuration for formation of the precursor120.

With the above-described barrier metal film production apparatus, thebarrier metal film 123 can be formed uniformly to a small thickness.Consequently, the barrier metal film 123 can be formed highly accuratelyat a high speed with excellent burial properties in a very smallthickness even to the interior of a tiny depression, for example severalhundred nanometers wide, which has been provided in the substrate 103.

Furthermore, the metal member 107 itself is applied as an electrode forplasma generation. Thus, there is no need for a plasma antenna aroundthe cylindrical portion of the chamber 101, and the degree of freedom ofthe surrounding construction can be increased.

A metal film production method and a metal film production apparatusaccording to the present invention will be described with reference tothe accompanying drawings. The metal film production method of thepresent invention involves a treatment for enhancing adhesion to abarrier metal layer of, for example, tantalum nitride (TaN) formed onthe surface of a substrate in order to prevent diffusion into thesubstrate.

According to a first aspect of the present invention, the barrier metalfilm of TaN is flattened by etching its surface with a diluent gas(e.g., argon: Ar) plasma. Further, the nitrogen atoms in the superficiallayer of the barrier metal film are removed using Ar⁺, therebydecreasing the nitrogen content of the superficial layer relative to theinterior of the matrix of the barrier metal film (this surface treatmentwill be referred to hereinafter as denitrification). The denitrificationbrings a state in which a film of a metal (Ta) is substantially formedin the superficial layer of the single-layer barrier metal film. In thismanner, a barrier metal film is produced highly efficiently and reliablyin a thin film condition, by use of an inexpensive gas having a highmass number, with the diffusion of the metal being prevented and theadhesion to the metal being maintained.

Depending on the material for the barrier metal film, it is possible toperform only the treatment for flattening the surface by etching it withthe diluent gas (e.g., argon: Ar) plasma while controlling the power ofthe plasma and the energization time. By so doing, adhesion can beimproved. As the barrier metal film, not only TaN, but tungsten nitrideor titanium nitride can be applied. As the diluent gas, not only Ar, buthelium, krypton, or neon can be applied.

The concrete construction of the apparatus according to the first aspectmay be as follows: A source gas containing a halogen (e.g., achlorine-containing gas) is supplied to the interior of a chamberbetween a substrate and an etched member made of Ta, and an atmospherewithin the chamber is converted into a plasma to generate a chlorine gasplasma. The etched member is etched with the chlorine gas plasma to forma precursor comprising the Ta component contained in the etched memberand the chlorine gas. Also, a nitrogen-containing gas is excited, andTaN, a metal nitride, is formed upon reaction between the excitednitrogen and the precursor. The resulting TaN is formed as a film on thesubstrate kept at a low temperature to form a barrier metal film. Thisprocess is performed using a barrier metal film production apparatus.After the barrier metal film is produced in this manner, an Ar gasplasma is generated within the chamber to carry out etching anddenitrification.

Alternatively, the concrete apparatus construction of the first aspectmay be as follows: A chlorine gas is supplied into a chamber, and anatmosphere within the chamber is converted into a plasma to generate achlorine gas plasma. An etched member made of copper (Cu) is etched withthe chlorine gas plasma to form a precursor comprising the Cu componentcontained in the etched member and chlorine inside the chamber. Thetemperature of the substrate is rendered lower than the temperature ofthe etched member to form a film of the Cu component of the precursor onthe substrate. This process is performed by use of a metal filmproduction apparatus. Before the substrate having the barrier metal filmof TaN formed thereon is housed in the chamber and the Cu component isformed as a film thereon, the Ar gas plasma is generated to carry outetching and denitrification.

FIG. 28 shows an outline of an apparatus for a film formation processfor forming a Cu film. As shown, for example, in FIG. 28, a handlingrobot 401 for transporting a substrate is installed at a central site.Around the robot 401, there are provided an accommodation device 402 foraccommodating the substrate, a barrier metal CVD 403 for forming abarrier metal film on the substrate, and a Cu-CVD 404 for forming a Cufilm. The robot 401 transports the substrate from the accommodationdevice 402 to the barrier metal CVD 403, from the barrier metal CVD 403to the Cu-CVD 404, and from the Cu-CVD 404 to the accommodation device402. With such an apparatus for the film formation process, the metalfilm production apparatus according to the first aspect is provided inthe Cu-CVD 404.

The metal film production apparatus in the first aspect may be providedin the barrier metal CVD 403, or a dedicated metal film productionapparatus according to the first aspect may be provided around the robot401.

Embodiments of the metal film production method and metal filmproduction apparatus according to the first aspect will be describedwith reference to the accompanying drawings, with the provision of theapparatus in the Cu-CVD 404 being taken as an example.

FIG. 29 is a schematic side view of a metal film production apparatusaccording to the fifteenth embodiment of the present invention. FIG. 30is a schematic construction drawing showing another example of diluentgas supply means. FIG. 31 shows the sectional status of a substrateillustrating a barrier metal film. FIGS. 32 and 33 show the conceptstatus of a barrier metal film in denitrification. The illustrated metalfilm production apparatus corresponds to the Cu-CVD 404 shown in FIG. 1.

As shown in FIG. 29, a support platform 202 is provided near the bottomof a cylindrical chamber 201 made of, say, a ceramic (an insulatingmaterial), and a substrate 203 is placed on the support platform 202.Temperature control means 206, as control means, equipped with a heater204 and refrigerant flow-through means 205 is provided in the supportplatform 202 so that the support platform 202 is controlled to apredetermined temperature (for example, a temperature at which thesubstrate 203 is maintained at 100 to 200° C.) by the temperaturecontrol means 206.

An upper surface of the chamber 201 is an opening, which is closed witha copper plate member 207, as an etched member, made of a metal. Theinterior of the chamber 201 closed with the copper plate member 207 ismaintained at a predetermined pressure by a vacuum device 208. A coiledplasma antenna 209 is provided around a cylindrical portion of thechamber 201. A matching instrument 210 and a power source 211 areconnected to the plasma antenna 209 to supply power. Plasma generationmeans is constituted by the plasma antenna 209, matching instrument 210and power source 211.

Nozzles 212 for supplying a source gas (a Cl₂ gas diluted with He or Arto a chlorine concentration of ≦50%, preferably about 10%), containingchlorine as a halogen, to the interior of the chamber 201 are connectedto the cylindrical portion of the chamber 201 above the support platform202. The nozzle 212 is fed with the source gas via a flow controller213. Within the chamber 201, the source gas is fed toward the copperplate member 207 (source gas supply means). Fluorine (F), bromine (Br)or iodine (I) can also be applied as the halogen to be incorporated intothe source gas.

With the above-described metal film production apparatus, the source gasis supplied from the nozzles 212 into the chamber 201, andelectromagnetic waves are shot from the plasma antenna 209 into thechamber 201, whereby the Cl₂ gas is ionized to generate a Cl₂ gas plasma(source gas plasma) 214. The pressure inside the chamber 201, set by thevacuum device 208, is such a high pressure that the plasma density ofthe Cl₂ gas plasma 214 will be higher toward the wall surface within thechamber 201. As means for increasing the plasma density of the Cl₂ gasplasma 214 on the wall surface side, the frequency of the power source211 may be increased.

The Cl₂ gas plasma 214 causes an etching reaction to the copper platemember 207, forming a precursor (Cu_(x)Cl_(y)) 215. At this time, thecopper plate member 207 is maintained by the Cl₂ gas plasma 214 at apredetermined temperature (e.g., 200 to 400° C.) which is higher thanthe temperature of the substrate 203.

The precursor (Cu_(x)Cl_(y)) 215 formed within the chamber 201 istransported toward the substrate 203 controlled to a lower temperaturethan the temperature of the copper plate member 207. The precursor(Cu_(x)Cl_(y)) 215 transported toward the substrate 203 is convertedinto only Cu ions by a reduction reaction, and directed at the substrate203 to form a thin Cu film 216 on the surface of the substrate 203.

The reactions involved can be expressed by:

2Cu+Cl₂→2CuCl→2Cu↓+Cl₂↑

The gases and the etching products that have not been involved in thereaction are exhausted through an exhaust port 217.

The source gas has been described, with the Cl₂ gas diluted with, say,He or Ar taken as an example. However, the Cl₂ gas can be used alone, oran HCl gas can also be applied. If the HCl gas is applied, an HCl gasplasma is generated as the source gas plasma. However, the precursorformed by etching of the copper plate member 207 is Cu_(x)Cl_(y). Thus,the source gas may be any gas containing chlorine, and a gas mixture ofan HCl gas and a Cl₂ gas is also usable. The material for the copperplate member 207 is not limited to copper (Cu), but it is possible touse a halide forming metal, preferably a chloride forming metal, such asAg, Au, Pt, Ta, Ti or W. In this case, the resulting precursor is ahalide (chloride) of Ag, Au, Pt, Ta, Ti or W, and the thin film formedon the surface of the substrate 203 is that of Ag, Au, Pt, Ta, Ti or W.

Since the metal film production apparatus constructed as above uses theCl₂ gas plasma (source gas plasma) 214, the reaction efficiency ismarkedly increased, and the speed of film formation is fast. Since theCl₂ gas is used as the source gas, moreover, the cost can be markedlydecreased. Furthermore, the substrate 203 is controlled to a lowertemperature than the temperature of the copper plate member 207 by useof the temperature control means 206. Thus, the amounts of impurities,such as chlorine, remaining in the thin Cu film 216 can be decreased, sothat a high quality thin Cu film 216 can be produced.

Furthermore, the plasma density of the Cl₂ gas plasma 214 is higher onthe wall surface side. Thus, a high density Cl₂ gas plasma 214 can begenerated, thus making the film formation speed remarkably high. Evenwhen a large chamber 201 is used, namely, even for a large substrate203, a thin Cu film 216 can be formed.

Diluent gas nozzles 221 are provided, as diluent gas supply means, forsupplying an Ar gas, as a diluent gas, to the interior of the chamber201 above the surface of the substrate 203. The Ar gas is supplied fromthe diluent gas nozzle 221, and electromagnetic waves are shot from theplasma antenna 209 into the chamber 201, whereby the Ar gas is ionizedto generate an Ar gas plasma (surface treatment plasma generationmeans). A bias power source 220 is connected to the support platform202, and a bias voltage is applied thereto for supporting the substrate203 on the support platform 202.

In connection with the diluent gas supply means, when the Ar gas isapplied as a diluent gas for the Cl₂ gas, a control valve 222 may beprovided at the site of merger between the source gas (Cl₂ gas) and thediluent gas (Ar gas), as shown in FIG. 30. By so doing, the Cl₂ gas maybe stopped during generation of the Ar gas plasma, and only the Ar gasmay be supplied through the nozzle 212. According to this construction,there is no need for the provision of the diluent gas nozzle 221,presenting advantage in space.

On the surface of the substrate 203 carried into the above-describedmetal film production apparatus, the barrier metal film 223 of TaN hasbeen formed, as shown in FIG. 31. By generating the Ar gas plasma, thebarrier metal film 223 on the surface of the substrate 203 is etchedwith Ar⁺ to flatten the barrier metal film 223. Also, denitrification isperformed in which the nitrogen atoms (N) of the TaN in the superficiallayer of the barrier metal film 223 are removed to decrease the nitrogencontent of the superficial layer relative to the interior of the matrixof the barrier metal film 223. As the barrier metal film 223, WN or TiNcan also be applied.

The flattening of the barrier metal film 223 and its denitrificationupon generation of the Ar gas plasma are carried out before formation ofthe aforementioned thin Cu film 216. That is, when the substrate 203having the barrier metal film 223 of TaN formed thereon is received ontothe support platform 202, the Ar gas is supplied from the diluent gasnozzles 221 prior to the formation of the thin Cu film 216. At the sametime, electromagnetic waves are shot from the plasma antenna 209 intothe chamber 201 to generate an Ar gas plasma.

Upon generation of the Ar gas plasma, the surface of the barrier metalfilm 223 is etched with Ar⁺ for flattening. As shown in FIG. 32, thebarrier metal film 223 comprises Ta and N in an amorphous state. In thisstate, N of a lower mass is preferentially removed by Ar⁺, so that thesuperficial layer of the barrier metal film 223 (for example, up to ahalf, preferably about a third, of the entire film thickness) isdenitrified. As a result, there emerges the barrier metal film 223 of atwo-layer structure, a metal layer 223 a substantially composed of Ta,and a TaN layer 223 b, as shown in FIG. 33. On this occasion, the entirefilm thickness of the barrier metal film 223 remains the film thicknesshaving the single layer.

To increase the amount of Ar⁺ generated, control is exercised forincreasing the voltage applied to the plasma antenna 209, or forincreasing the flow rate of the Ar gas. To draw in Ar⁺ toward thesubstrate 203, the bias power source 220 is controlled to lower thepotential of the substrate 203 to the negative side. For this purpose,schedule control is easy to effect according to a preset schedule. Whiledenitrification is taking place, the depth distribution of the metallayer 223 a is measured. Control over the voltage of the plasma antenna209 or the flow rate of the Ar gas, or control of the bias power source220 can be exercised based on the results of the measurement.

After denitrification is performed, the sites of N removed become voids,creating irregularities on the atomic level. Thus, it is preferred todensify the remaining Ta atoms. To make the Ta atoms dense, the presentembodiment uses a heater 204 to heat the substrate 203 for heattreatment, thereby densifying the Ta atoms (densification means). Theheat treatment is performed to such a degree that the atoms do not takea crystal structure (the atoms maintain an amorphous state). Thedensification means may be plasma heating for heating the substrate 203.

With the foregoing metal film production apparatus, the Ar gas plasma isgenerated within the chamber 201 accommodating the substrate 203 havingthe barrier metal film 223 formed thereon. The Ar gas plasma etches thebarrier metal film 223 to flatten it. The Ar gas plasma also removes thenitrogen atoms to denitrify the barrier metal film 223. Thus, thereappears the barrier metal film 223 with a two-layer structure, i.e., themetal layer 223 a composed substantially of Ta and the TaN layer 223 b.Moreover, the entire film thickness can remain the single-layer filmthickness. Hence, the barrier metal film 223 can be in a two-layerstructure state without becoming thick, and yet the metal layer 223 acan retain adhesion to the thin Cu film 216, while the TaN layer 223 bcan prevent diffusion of Cu. Consequently, the thin Cu film 216 can beformed, with satisfactory adhesion, without diffusion into the substrate203, so that the Cu wiring process can be stabilized.

A barrier metal film production method and a barrier metal filmproduction apparatus according to the sixteenth embodiment of thepresent invention will be described with reference to FIGS. 34 to 36.FIG. 34 is a schematic side view of the metal film production apparatusaccording to the sixteenth embodiment of the present invention. FIG. 35is a view taken along the arrowed line VIII-VIII of FIG. 34. FIG. 36 isa view taken along the arrowed line IX-IX of FIG. 35. The same membersas the members illustrated in FIG. 29 are assigned the same numerals,and duplicate explanations are omitted.

An upper surface of the chamber 201 is an opening, which is closed witha disk-shaped ceiling board 230 made of an insulating material (forexample, a ceramic). An etched member 231 made of a metal (copper, Cu)is interposed between the opening at the upper surface of the chamber201 and the ceiling board 230. The etched member 231 is provided with aring portion 232 fitted to the opening at the upper surface of thechamber 201. A plurality of (12 in the illustrated embodiment)protrusions 233, which extend close to the center in the diametricaldirection of the chamber 201 and have the same width, are provided inthe circumferential direction on the inner periphery of the ring portion232.

The protrusions 233 are integrally or removably attached to the ringportion 232. Notches (spaces) 235 formed between the protrusions 233 arepresent between the ceiling board 230 and the interior of the chamber201. The ring portion 232 is earthed, and the plural protrusions 233 areelectrically connected together and maintained at the same potential.Temperature control means (not shown), such as a heater, is provided inthe etched member 231 to control the temperature of the etched member231 to 200 to 400° C., for example.

Second protrusions shorter in the diametrical direction than theprotrusions 233 can be arranged between the protrusions 233. Moreover,short protrusions can be arranged between the protrusion 233 and thesecond protrusion. By so doing, the area of copper, an object to beetched, can be secured, with an induced current being suppressed.

A planar winding-shaped plasma antenna 234, for converting theatmosphere inside the chamber 201 into a plasma, is provided above theceiling board 230. The plasma antenna 234 is formed in a planar ringshape parallel to the surface of the ceiling board 230. A matchinginstrument 210 and a power source 211 are connected to the plasmaantenna 234 to supply power. The etched member 231 has the plurality ofprotrusions 233 provided in the circumferential direction on the innerperiphery of the ring portion 232, and includes the notches (spaces) 235formed between the protrusions 233. Thus, the protrusions 233 arearranged between the substrate 203 and the ceiling board 230 in adiscontinuous state relative to the flowing direction of electricity inthe plasma antenna 234.

With the above-described metal film production apparatus, the source gasis supplied through the nozzles 212 to the interior of the chamber 201,and electromagnetic waves are shot from the plasma antenna 234 into thechamber 201. As a result, the Cl₂ gas is ionized to generate a Cl₂ gasplasma (source gas plasma) 214. The etched member 231, an electricconductor, is present below the plasma antenna 234. However, the Cl₂ gasplasma 214 occurs stably between the etched member 231 and the substrate203, namely, below the etched member 231, under the following action:

The action by which the Cl₂ gas plasma 214 is generated below the etchedmember 231 will be described. As shown in FIG. 36, a flow A ofelectricity in the plasma antenna 234 of the planar ring shape crossesthe protrusions 233. At this time, an induced current B occurs on thesurface of the protrusion 233 opposed to the plasma antenna 234. Sincethe notches (spaces) 235 are present in the etched member 231, theinduced current B flows onto the lower surface of each protrusion 233,forming a flow a in the same direction as the flow A of electricity inthe plasma antenna 234 (Faraday shield).

When the etched member 231 is viewed from the substrate 203, therefore,there is no flow in a direction in which the flow A of electricity inthe plasma antenna 234 is canceled out. Furthermore, the ring portion232 is earthed, and the protrusions 233 are maintained at the samepotential. Thus, even though the etched member 231, an electricconductor, exists, the electromagnetic wave is reliably thrown from theplasma antenna 234 into the chamber 201. Consequently, the Cl₂ gasplasma 214 is stably generated below the etched member 231.

The Cl₂ gas plasma 214 causes an etching reaction to the etched member231 made of copper, forming a precursor (Cu_(x)Cl_(y)) 215. At thistime, the etched member 231 is maintained by the Cl₂ gas plasma 214 at apredetermined temperature (e.g., 200 to 400° C.) which is higher thanthe temperature of the substrate 203. The precursor (Cu_(x)Cl_(y)) 215formed within the chamber 201 is transported toward the substrate 203controlled to a lower temperature than the temperature of the etchedmember 231. The precursor (Cu_(x)Cl_(y)) 215 transported toward thesubstrate 203 is converted into only Cu ions by a reduction reaction,and directed at the substrate 203 to form a thin Cu film 216 on thesurface of the substrate 203.

The reactions involved are the same as in the aforementioned fifteenthembodiment. The gases and the etching products, which have not beeninvolved in the reactions, are exhausted through an exhaust port 217.

Since the metal film production apparatus constructed as above uses theCl₂ gas plasma (source gas plasma) 214, the reaction efficiency ismarkedly increased, and the speed of film formation is fast. Since theCl₂ gas is used as the source gas, moreover, the cost can be markedlydecreased. Furthermore, the substrate 203 is controlled to a lowertemperature than the temperature of the etched member 231 by use of thetemperature control means 206. Thus, the amounts of impurities, such aschlorine, remaining in the thin Cu film 216 can be decreased, so that ahigh quality thin Cu film 216 can be produced.

In addition, the etched member 231 has the plurality of protrusions 233provided in the circumferential direction on the inner periphery of thering portion 232, and includes the notches (spaces) 235 formed betweenthe protrusions 233. Thus, the induced currents generated in the etchedmember 231 flow in the same direction as the flowing direction ofelectricity in the plasma antenna 234, when viewed from the substrate203. Therefore, even though the etched member 231, an electricconductor, exists below the plasma antenna 234, the electromagneticwaves are reliably thrown from the plasma antenna 234 into the chamber201. Consequently, the Cl₂ gas plasma 214 can be stably generated belowthe etched member 231.

Diluent gas nozzles 221 are provided, as diluent gas supply means, forsupplying an Ar gas, as a diluent gas, to the interior of the chamber201 above the surface of the substrate 203. The Ar gas is supplied fromthe diluent gas nozzle 221, and electromagnetic waves are shot from theplasma antenna 234 into the chamber 201, whereby the Ar gas is ionizedto generate an Ar gas plasma (surface treatment plasma generationmeans). A bias power source 220 is connected to the support platform202, and a bias voltage is applied thereto for supporting the substrate203 on the support platform 202.

On the surface of the substrate 203 admitted into the above-describedmetal film production apparatus, the barrier metal film 223 of TaN hasbeen formed, as shown in FIG. 31. By generating the Ar gas plasma, thebarrier metal film 223 on the surface of the substrate 203 is etchedwith Ar⁺ to flatten the barrier metal film 223. Also, denitrification isperformed in which the nitrogen atoms (N) of the TaN in the superficiallayer of the barrier metal film 223 are removed to decrease the nitrogencontent of the superficial layer relative to the interior of the matrixof the barrier metal film 223. As the barrier metal film 223, WN or TiNcan also be applied.

The flattening of the barrier metal film 223 and its denitrificationupon generation of the Ar gas plasma are carried out before formation ofthe aforementioned thin Cu film 216. The details of the flattening ofthe barrier metal film 223, and the details of the denitrification ofthis film are the same as in the fifteenth embodiment, and relevantexplanations are omitted.

With the foregoing metal film production apparatus, as in the fifteenthembodiment, the barrier metal film 223 can be in a two-layer structurestate without becoming thick, and yet the metal layer 223 a can retainadhesion to the thin Cu film 216, while the TaN layer 223 b can preventdiffusion of Cu. Consequently, the thin Cu film 216 can be formed, withsatisfactory adhesion, without diffusion into the substrate 203, so thatthe Cu wiring process can be stabilized.

A metal film production method and a metal film production apparatusaccording to the seventeenth embodiment of the present invention will bedescribed with reference to FIG. 37. FIG. 37 is a schematic side view ofthe metal film production apparatus according to the seventeenthembodiment of the present invention. The same members as the membersillustrated in FIGS. 2 and 7 are assigned the same numerals, andduplicate explanations are omitted.

The opening of an upper portion of a chamber 201 is closed with aceiling board 230, for example, made of a ceramic (an insulatingmaterial). An etched member 241 made of a metal (copper, Cu) is providedon a lower surface of the ceiling board 230, and the etched member 241is of a quadrangular pyramidal shape. Slit-shaped opening portions 242are formed at a plurality of locations (for example, four locations) inthe periphery of an upper part of the cylindrical portion of the chamber201, and one end of a tubular passage 243 is fixed to each of theopening portions 242. A tubular excitation chamber 244 made of aninsulator is provided halfway through the passage 243, and a coiledplasma antenna 245 is provided around the excitation chamber 244. Theplasma antenna 245 is connected to a matching instrument 248 and a powersource 249 to receive power. The plasma antenna 245, the matchinginstrument 248 and the power source 249 constitute plasma generationmeans.

A flow controller 246 is connected to the other end of the passage 243,and a chlorine-containing source gas (a Cl₂ gas diluted with He or Ar toa chlorine concentration of ≦50%, preferably about 10%) is supplied intothe passage 243 via the flow controller 246. By shooting electromagneticwaves from the plasma antenna 245 into the excitation chamber 244, theCl₂ gas is ionized to generate a Cl₂ gas plasma (source gas plasma) 247.Because of the generation of the Cl₂ gas plasma 247, excited chlorine isfed into the chamber 201 through the opening portion 42, whereupon theetched member 241 is etched with excited chlorine.

With the above-described metal film production apparatus, the source gasis supplied into the passage 243 via the flow controller 246 and fedinto the excitation chamber 244. By shooting electromagnetic waves fromthe plasma antenna 245 into the excitation chamber 244, the Cl₂ gas isionized to generate a Cl₂ gas plasma (source gas plasma) 247. Since apredetermined differential pressure has been established between thepressure inside the chamber 201 and the pressure inside the excitationchamber 244 by the vacuum device 208, the excited chlorine of the Cl₂gas plasma 247 in the excitation chamber 244 is fed to the etched member241 inside the chamber 201 through the opening portion 242. The excitedchlorine causes an etching reaction to the etched member 241, forming aprecursor (M_(x)Cl_(y)) 215 inside the chamber 201.

At this time, the etched member 241 is maintained at a predeterminedtemperature (e.g., 200 to 400° C.), which is higher than the temperatureof the substrate 203, by a heater 250. The precursor (Cu_(x)Cl_(y)) 215formed inside the chamber 201 is transported toward the substrate 203controlled to a lower temperature than the temperature of the etchedmember 241. The precursor (Cu_(x)Cl_(y)) 215 transported toward thesubstrate 203 is converted into only Cu ions by a reduction reaction,and directed at the substrate 203 to form a thin Cu film 216 on thesurface of the substrate 203.

The reactions on this occasion are the same as in the aforementionedfifteenth embodiment, and the gases and etching products that have notbeen involved in the reactions are exhausted through an exhaust port217.

With the above-described metal film production apparatus, the Cl₂ gasplasma 247 is generated in the excitation chamber 244 isolated from thechamber 201. Thus, the substrate 203 is not exposed to the plasma anymore, and the substrate 203 becomes free from damage from the plasma. Asthe means for generating the Cl₂ gas plasma 247 in the excitationchamber 244, it is possible to use microwaves, laser, electron rays, orsynchrotron radiation. It is also permissible to form the precursor byheating a metal filament to a high temperature. The construction forisolating the Cl₂ gas plasma 247 from the substrate 203 may be theprovision of the excitation chamber 244 in the passage 243, or may beother construction, for example, the isolation of the chamber 201.

The above-described metal film production apparatus is provided withdiluent gas nozzles 221, as diluent gas supply means, for supplying anAr gas, as a diluent gas, to the interior of the chamber 201 above thesurface of the substrate 203. A coil-shaped surface treatment plasmaantenna 236 is provided on a trunk portion of the chamber 201. Amatching instrument 237 and a power source 238 are connected to thesurface treatment plasma antenna 236 to supply power. The Ar gas issupplied from the diluent gas nozzles 221, and electromagnetic waves areshot from the plasma antenna 236 into the chamber 201, whereby the Argas is ionized to generate an Ar gas plasma (surface treatment plasmageneration means). A bias power source 220 is connected to the supportplatform 202, and a bias voltage is applied thereto for supporting thesubstrate 203 on the support platform 202.

On the surface of the substrate 203 admitted into the above-describedmetal film production apparatus, a barrier metal film 223 of TaN hasbeen formed, as shown in FIG. 31. By generating the Ar gas plasma, thebarrier metal film 223 on the surface of the substrate 203 is etchedwith Ar⁺ to flatten the barrier metal film 223. Also, denitrification isperformed in which the nitrogen atoms (N) of the TaN in the superficiallayer of the barrier metal film 223 are removed to decrease the nitrogencontent of the superficial layer relative to the interior of the matrixof the barrier metal film 223. As the barrier metal film 223, WN or TiNcan also be applied.

The flattening of the barrier metal film 223 and its denitrificationupon generation of the Ar gas plasma are carried out before formation ofthe aforementioned thin Cu film 216. The details of the flattening ofthe barrier metal film 223 and the denitrification of this film are thesame as in the fifteenth embodiment, and relevant explanations areomitted.

With the foregoing metal film production apparatus, the barrier metalfilm 223 can be in a two-layer structure state without becoming thick,and yet the metal layer 223 a (see FIG. 33) can retain adhesion to thethin Cu film 216, while the TaN layer 223 b (see FIG. 33) can preventdiffusion of Cu. Consequently, the thin Cu film 216 can be formed, withsatisfactory adhesion, without diffusion into the substrate 203, so thatthe Cu wiring process can be stabilized.

A barrier metal film production method and a barrier metal filmproduction apparatus according to the eighteenth embodiment of thepresent invention will be described with reference to FIG. 38. FIG. 38is a schematic side view of the metal film production apparatusaccording to the eighteenth embodiment of the present invention. Thesame members as the members illustrated in FIGS. 29, 34 and 37 areassigned the same numerals, and duplicate explanations are omitted.

Compared with the metal film production apparatus of the fifteenthembodiment shown in FIG. 29, the plasma antenna 209 is not providedaround the cylindrical portion of the chamber 201, and the matchinginstrument 210 and power source 211 are connected to the copper platemember 207 for supply of power to the copper plate member 207. With theabove-described metal film production apparatus, the source gas issupplied from the nozzles 212 into the chamber 201, and electromagneticwaves are shot from the copper plate member 207 into the chamber 201,the Cl₂ gas is ionized to generate a Cl₂ gas plasma (source gas plasma)214. The Cl₂ gas plasma 214 causes an etching reaction to the copperplate member 207, forming a precursor (Cu_(x)Cl_(y)) 215. At this time,the copper plate member 207 is maintained at a predetermined temperature(e.g., 200 to 400° C.), which is higher than the temperature of thesubstrate 203, by the Cl₂ gas plasma 214.

The precursor (Cu_(x)Cl_(y)) 215 formed inside the chamber 201 istransported toward the substrate 203 controlled to a lower temperaturethan the temperature of the copper plate member 207. The precursor(Cu_(x)Cl_(y)) 215 transported toward the substrate 203 is convertedinto only Cu ions by a reduction reaction, and directed at the substrate203 to form a thin Cu film 216 on the surface of the substrate 203. Thereactions on this occasion are the same as in the aforementionedfifteenth embodiment, and the gases and etching products that have notbeen involved in the reactions are exhausted through an exhaust port217.

With the above-described metal film production apparatus, the copperplate member 207 itself is applied as an electrode for plasmageneration. Thus, the plasma antenna 209 intended to prepare the thin Cufilm 216 need not be provided around the cylindrical portion of thechamber 201.

The above-described metal film production apparatus is provided withdiluent gas nozzles 221, as diluent gas supply means, for supplying anAr gas, as a diluent gas, to the interior of the chamber 201 above thesurface of the substrate 203. Supply of the source gas through thenozzles 212 is cut off, the Ar gas is supplied from the diluent gasnozzles 221, and electromagnetic waves are shot from the copper platemember 207 into the chamber 201. By so doing, the Ar gas is ionized togenerate an Ar gas plasma (surface treatment plasma generation means). Abias power source 220 is connected to the support platform 202, and abias voltage is applied thereto for supporting the substrate 203 on thesupport platform 202.

On the surface of the substrate 203 admitted into the above-describedmetal film production apparatus, a barrier metal film 223 of TaN hasbeen formed, as shown in FIG. 31. By generating the Ar gas plasma, thebarrier metal film 223 on the surface of the substrate 203 is etchedwith Ar⁺ to flatten the barrier metal film 223. Also, denitrification isperformed in which the nitrogen atoms (N) of the TaN in the superficiallayer of the barrier metal film 223 are removed to decrease the nitrogencontent of the superficial layer relative to the interior of the matrixof the barrier metal film 223. As the barrier metal film 223, WN or TiNcan also be applied. As the surface treatment plasma generation means,it is permissible to provide a coiled surface treatment plasma antennaon the trunk portion of the chamber 201, and supply power via a matchinginstrument and a power source, thereby generating an Ar gas plasma.

The flattening of the barrier metal film 223 and its denitrificationupon generation of the Ar gas plasma are carried out before formation ofthe aforementioned thin Cu film 216. The details of the flattening ofthe barrier metal film 223 and the denitrification of this film are thesame as in the fifteenth embodiment, and relevant explanations areomitted.

With the foregoing metal film production apparatus, as in the fifteenthembodiment, the barrier metal film 223 can be in a two-layer structurestate without becoming thick, and the metal layer 223 a (see FIG. 33)can retain adhesion to the thin Cu film 216, while the TaN layer 223 b(see FIG. 33) can prevent diffusion of Cu. Consequently, the thin Cufilm 216 can be formed, with satisfactory adhesion, without diffusioninto the substrate 203, so that the Cu wiring process can be stabilized.

Next, an example in which embodiments of the metal film productionmethod and metal film production apparatus according to the first aspectare provided in the barrier metal CVD 403 will be described withreference to FIG. 39. FIG. 39 schematically shows a side view of themetal film production apparatus according to the nineteenth embodimentof the present invention.

As shown in the drawing, a support platform 252 is provided near thebottom of a cylindrical chamber 251 made of, say, a ceramic (aninsulating material), and a substrate 253 is placed on the supportplatform 252. Temperature control means 256 equipped with a heater 254and refrigerant flow-through means 255 is provided in the supportplatform 252 so that the support platform 252 is controlled to apredetermined temperature (for example, a temperature at which thesubstrate 253 is maintained at 100 to 200° C.) by the temperaturecontrol means 256.

An upper surface of the chamber 251 is an opening, which is closed witha metal member 257, as an etched member, made of a metal (e.g., W, Ti,Ta, or TiSi). The interior of the chamber 251 closed with the metalmember 257 is maintained at a predetermined pressure by a vacuum device258. A plasma antenna 259, as a coiled winding antenna of plasmageneration means, is provided around a cylindrical portion of thechamber 251. A matching instrument 260 and a power source 261 areconnected to the plasma antenna 259 to supply power.

Nozzles 262 for supplying a source gas (a Cl₂ gas diluted with He or Arto a chlorine concentration of ≦50%, preferably about 10%), containingchlorine as a halogen, to the interior of the chamber 251 are connectedto the cylindrical portion of the chamber 251 below the metal member257. The nozzle 262 is open toward the horizontal, and is fed with thesource gas via a flow controller 263 (halogen gas supply means).Fluorine (F), bromine (Br) or iodine (I) can also be applied as thehalogen to be incorporated into the source gas.

Slit-shaped opening portions 264 are formed at a plurality of locations(for example, four locations) in the periphery of a lower part of thecylindrical portion of the chamber 251, and one end of a tubular passage265 is fixed to each of the opening portions 264. A tubular excitationchamber 266 made of an insulator is provided halfway through the passage265, and a coiled plasma antenna 267 is provided around the excitationchamber 266. The plasma antenna 267 is connected to a matchinginstrument 268 and a power source 269 to receive power. The plasmaantenna 267, the matching instrument 268 and the power source 269constitute excitation means. A flow controller 270 is connected to theother end of the passage 265, and an ammonia gas (NH₃ gas) as anitrogen-containing gas is supplied into the passage 265 via the flowcontroller 270.

With the above-described metal film production apparatus, the source gasis supplied through the nozzles 262 to the interior of the chamber 251,and electromagnetic waves are shot from the plasma antenna 259 into thechamber 251. As a result, the Cl₂ gas is ionized to generate a Cl₂ gasplasma (source gas plasma) 271. The Cl₂ gas plasma 271 causes an etchingreaction to the metal member 257, forming a precursor (M_(x)Cl_(y): M isa metal such as W, Ti, Ta or TiSi) 272.

Separately, the NH₃ gas is supplied into the passage 265 via the flowcontroller 270 and fed into the excitation chamber 266. By shootingelectromagnetic waves from the plasma antenna 267 into the excitationchamber 266, the NH₃ gas is ionized to generate an NH₃ gas plasma 263.Since a predetermined differential pressure has been established betweenthe pressure inside the chamber 251 and the pressure inside theexcitation chamber 266 by the vacuum device 258, the excited ammonia ofthe NH₃ gas plasma 273 in the excitation chamber 266 is fed to theprecursor (M_(x)Cl_(y)) 272 inside the chamber 251 through the openingportion 264.

That is, excitation means for exciting the nitrogen-containing gas inthe excitation chamber 266 isolated from the chamber 251 is constructed.Because of this construction, the metal component of the precursor(M_(x)Cl_(y)) 272 and ammonia react to form a metal nitride (MN)(formation means). At this time, the metal member 257 and the excitationchamber 266 are maintained by the plasmas at predetermined temperatures(e.g., 200 to 400° C.) which are higher than the temperature of thesubstrate 253.

The metal nitride (MN) formed within the chamber 251 is transportedtoward the substrate 253 controlled to a low temperature, whereby a thinMN film 274 (a TaN film if the metal member 257 of Ta is applied) isformed on the surface of the substrate 253.

The reaction for formation of the thin MN film 274 can be expressed by:

2MCl+2NH₃→2MN↓+HCl↑+2H₂↑

The gases and the etching products that have not been involved in thereactions are exhausted through an exhaust port 277.

The source gas has been described, with the Cl₂ gas diluted with, say,He or Ar taken as an example. However, the Cl₂ gas can be used alone, oran HCl gas can also be applied. When the HCl gas is applied, an HCl gasplasma is generated as the source gas plasma. Thus, the source gas maybe any gas containing chlorine, and a gas mixture of an HCl gas and aCl₂ gas is also usable. As the material for the metal member 257, it ispossible to use an industrially applicable metal such as Ag, Au, Pt orSi. Further, the NH₃ gas is supplied into the passage 265 and fed intothe excitation chamber 266. At the same time, electromagnetic waves areshot from the plasma antenna 267 into the excitation chamber 266 togenerate the NH₃ gas plasma 263. However, an NH₃ gas plasma can begenerated within the chamber 251 by supplying an NH₃ gas into thechamber 251 and supplying power to the plasma antenna 259. In this case,the chamber 265, excitation chamber 266, plasma antenna 267, matchinginstrument 268 and power source 269 can be omitted.

With the above-described metal film production apparatus, the metal isformed by plasmas to produce the thin MN film 274 as the barrier metalfilm. Thus, the barrier metal film can be formed uniformly to a smallthickness. Consequently, the barrier metal film can be formed highlyaccurately at a high speed with excellent burial properties in a verysmall thickness even to the interior of a tiny depression, for example,several hundred nanometers wide, which has been provided in thesubstrate 253.

The above-described metal film production apparatus is provided withdiluent gas nozzles 276, as diluent gas supply means, for supplying anAr gas, as a diluent gas, to the interior of the chamber 251 above thesurface of the substrate 253. The Ar gas is supplied from the diluentgas nozzles 276, and electromagnetic waves are shot from the plasmaantenna 259 into the chamber 251, whereby the Ar gas is ionized togenerate an Ar gas plasma (surface treatment plasma generation means). Abias power source 277 is connected to the support platform 252, and abias voltage is applied thereto for supporting the substrate 253 on thesupport platform 252.

With the above-described metal film production apparatus, the thin MNfilm 274 as a barrier metal film is formed, whereafter an Ar gas plasmais generated. By generating the Ar gas plasma, the barrier metal film onthe surface of the substrate 253 is etched with Ar⁺ to flatten thebarrier metal film. Also, denitrification is performed in which thenitrogen atoms (N) of the TaN in the superficial layer of the barriermetal film are removed. After flattening of the barrier metal film andthe removal of the nitrogen atoms (N) of the TaN in the superficiallayer for denitrification, a thin copper (Cu) film or a thin aluminum(Al) film is formed on the barrier metal film by a film forming device.The details of the flattening of the barrier metal film and thedenitrification of this film upon generation of the Ar gas plasma arethe same as in the fifteenth embodiment. Thus, relevant explanations areomitted.

With the foregoing metal film production apparatus, as in the fifteenthembodiment, the barrier metal film can be in a two-layer structure statewithout becoming thick, and the resulting metal layer can retainadhesion to a thin metal film formed by film formation in the subsequentstep. Whereas the TaN layer can prevent diffusion of metal during filmformation in the subsequent step. Consequently, the thin metal film(thin Cu film) during film formation in the subsequent step can beformed, with satisfactory adhesion, without diffusion into the substrate253, so that the Cu wiring process can be stabilized.

The construction of the metal film production apparatus for producingthe barrier metal film may employ a device of the type generating acapacitive coupling plasma, or a device of the remote type whichgenerates a plasma in a manner isolated from a film formation chamber.

Next, the second aspect of the present invention will be described.According to the second aspect, the barrier metal film of TaN issubjected to a surface treatment in which this film is reacted in areducing gas (e.g. hydrogen gas) atmosphere (a hydrogen gas plasma) toremove the nitrogen atoms in the superficial layer of the barrier metalfilm, thereby decreasing the nitrogen content of the superficial layerrelative to the interior of the matrix of the barrier metal film (thistreatment will be referred to hereinafter as denitrification). Thedenitrification brings a state in which a film of the metal (Ta) issubstantially formed in the superficial layer of the single-layerbarrier metal film. In this manner, a barrier metal film is producedhighly efficiently and reliably in a thin film condition, with thediffusion of the metal being prevented and the adhesion to the metalbeing maintained.

As the reducing gas, a nitrogen gas as well as the hydrogen gas can beapplied, or a carbon monoxide gas can also be applied. If the carbonmonoxide gas is used, denitrification can be carried out in a carbonmonoxide gas atmosphere, without generation of plasma.

The concrete construction of the apparatus according to the secondaspect of the invention may be as follows: A source gas containing ahalogen (e.g., a chlorine-containing gas) is supplied to the interior ofa chamber between a substrate and an etched member of Ta, and anatmosphere within the chamber is converted into a plasma to generate achlorine gas plasma. The etched member is etched with the chlorine gasplasma to form a precursor comprising the Ta component contained in theetched member and the chlorine gas. Also, a nitrogen-containing gas isexcited, and TaN, a metal nitride, is formed upon reaction between theexcited nitrogen and the precursor. The resulting TaN is formed as afilm on the substrate kept at a low temperature to form a barrier metalfilm. This process is performed using a barrier metal film productionapparatus. After the barrier metal film is produced in this manner, ahydrogen gas plasma (or a nitrogen gas plasma) is generated within thechamber to react radical hydrogen with nitrogen, performingdenitrification. That is, the barrier metal film production apparatusshown in FIG. 39 can be applied.

Alternatively, the concrete construction of the apparatus of the secondaspect may be as follows: A chlorine gas is supplied into the chamber,and an atmosphere within the chamber is converted into a plasma togenerate a chlorine gas plasma. An etched member made of copper (Cu) isetched with the chlorine gas plasma to form a precursor comprising theCu component contained in the etched member and chlorine inside thechamber. The temperature of the substrate is rendered lower than thetemperature of the etched member to form a film of the Cu component ofthe precursor on the substrate. This process is performed using a metalfilm forming device. Before the substrate having a barrier metal film ofTaN formed thereon is housed in the chamber and the Cu component isformed as a film thereon, a hydrogen gas plasma (or a nitrogen gasplasma) is generated within the chamber to react radical hydrogen withnitrogen, performing denitrification. That is, the metal film productionapparatus shown, for example, in FIGS. 29, 34, 37 and 38 can be applied.

Embodiments of the metal film production method and metal filmproduction apparatus according to the second aspect will be described,with the provision of the apparatus in the Cu-CVD 404 (see FIG. 28)being taken as an example.

FIG. 40 shows the conceptual construction of a metal film productionapparatus according to the twentieth embodiment of the presentinvention. FIG. 41 shows the concept status of the barrier metal film indenitrification. The illustrated metal film production apparatus has theconceptual construction of the metal film production apparatus accordingto the fifteenth embodiment shown in FIG. 29, in which the gas suppliedthrough the nozzle 21 is different. Thus, the formation of the thin Cufilm in the metal film production apparatus is the same, and itsexplanation is omitted hereinbelow.

As shown in FIG. 40, reducing gas nozzles 225 are provided, as reducinggas supply means, for supplying a hydrogen gas (H₂ gas) as a reducinggas, to the interior of a chamber 201 above the surface of a substrate203. The H₂ gas is supplied from the reducing gas nozzles 225, andelectromagnetic waves are shot from a plasma antenna 209 into thechamber 201, whereby the H₂ gas is ionized to generate an H₂ gas plasma(surface treatment means). On the surface of the substrate 203 admittedinto the illustrated metal film production apparatus, a barrier metalfilm 223 of TaN (see FIG. 31) has been formed. Upon generation of the H₂gas plasma, hydrogen radicals H* react with the nitrogen atoms (N) ofthe TaN in the superficial layer of the substrate 203, forming ammoniaNH₃, which is exhausted. Thus, the nitrogen atoms (N) in the superficiallayer are removed to decrease the nitrogen content of the superficiallayer relative to the interior of the matrix of the barrier metal film223 (denitrification).

The denitrification of the barrier metal film 223 (see FIG. 31) causedby generation of the H₂ gas plasma is performed before formation of thethin Cu film 216 explained in the fifteenth embodiment of FIG. 29. Thatis, when the substrate 203 having the barrier metal film 223 of TaN (seeFIG. 31) formed thereon is admitted onto a support platform 202, the H₂gas is supplied from the reducing gas nozzles 225 prior to the formationof the thin Cu film 216 (see FIG. 29). At the same time, electromagneticwaves are shot from the plasma antenna 209 into the chamber 201, wherebythe H₂ gas plasma is generated.

Upon generation of the H₂ gas plasma, hydrogen radicals H* react withthe nitrogen atoms (N) of the TaN in the superficial layer of thesubstrate 203, forming ammonia NH₃, which is exhausted. The hydrogenradicals H* do not affect the metal, but react with only the nitrogenatoms (N), thereby forming ammonia NH₃.

That is, the reaction

N+3H*→NH₃

forms ammonia NH₃, which is exhausted.

As shown in FIG. 41, the barrier metal film 223 comprises Ta and N in anamorphous state. In this state, hydrogen radicals H* react with N,forming ammonia NH₃, which is exhausted. In this manner, the superficiallayer of the barrier metal film 223 (for example, up to a half,preferably about a third, of the entire film thickness) is denitrified.As a result, there emerges the barrier metal film 223 of a two-layerstructure, a metal layer 223 a substantially composed of Ta, and a TaNlayer 223 b, as shown in FIG. 33. On this occasion, the entire filmthickness of the barrier metal film 223 remains the film thicknessconstructed by the single layer.

Hydrogen radicals H* have a short life and penetrate narrow sites. Thus,the pressure inside the chamber 201 is lowered to decrease the density,or the temperature of the substrate 203 is controlled, thereby making itpossible to increase hydrogen radicals H* (prevent them from collidingwith each other), or to control the depth of the metal layer 223 acomposed substantially of Ta (see FIG. 33). Setting of the pressure canbe performed by increasing the mean free path (MFP) which is the valueof the distance traveled by a hydrogen radical H* before collision.Normally, the distance from the center of the plasma to the substrate203 depends on the apparatus. To increase the mean free path, control isexercised, with the pressure inside the chamber 201 being lowered. Ifthe apparatus has the support platform 202 movable upward and downward,the support platform 202 is raised, without a fall in the pressure, tobring the substrate 203 close to the center of the plasma, whereby themean free path can be increased relatively.

With the foregoing metal film production apparatus, the hydrogen gasplasma is generated within the chamber 201 accommodating the substrate203 having the barrier metal film 223 formed thereon. The hydrogenradicals H* take part in denitrification in which they react with thenitrogen atoms (N), forming ammonia NH₃, which is exhausted. Thus, therecan appear the barrier metal film 223 with a two-layer structure, i.e.,the metal layer 223 a composed substantially of Ta (see FIG. 33) and theTaN layer 223 b (see FIG. 33). Moreover, the entire film thickness canremain the single-layer film thickness. Hence, the barrier metal film223 can be in a two-layer structure state without becoming thick, andyet the metal layer 223 a (see FIG. 33) can retain adhesion to the thinCu film 216 (see FIG. 29), while the TaN layer 223 b (see FIG. 33) canprevent diffusion of Cu. Consequently, the thin Cu film 216 (see FIG.29) can be formed, with satisfactory adhesion, without diffusion intothe substrate 203, so that the Cu wiring process can be stabilized. Inaddition, denitrification can be carried out with high efficiency.

The hydrogen gas has been taken as an example of the reducing gas forthe purpose of explanation. In the case of the metal film productionapparatus in which a hydrogen atmosphere is not usable, a nitrogen gascan be used as the reducing gas. In this case, a nitrogen gas plasma isgenerated, whereupon N* reacts with the nitrogen atoms (N) of thebarrier metal film 223. As a result, N+N*→N₂, which is exhausted. Theuse of the nitrogen gas enables denitrification to take place easily,even if a limitation is imposed on the use of the reducing gas.

Alternatively, a carbon monoxide gas can be used as the reducing gas. Inthis case, no plasma is generated, and in the unchanged atmosphere, COreacts with the nitrogen atoms (N) of the barrier metal film 223, as in2N+2CO→2CN+O₂, which are exhausted. The use of the carbon monoxide gasenables denitrification to take place, simply by temperature control ofthe substrate 203 without generation of a plasma. Thus, consumption ofpower can be decreased.

The twentieth embodiment described above can be applied to the metalfilm production apparatuses of the sixteenth to eighteenth embodimentsshown in FIGS. 34, 37 and 38. It is also applicable to the barrier metalfilm production apparatus of the nineteenth embodiment shown in FIG. 39.It is also possible to combine the flattening of the surface with Ar⁺upon generation of the Ar gas plasma in the fifteenth to nineteenthembodiments with denitrification using the reducing gas plasma. In thiscase, an Ar gas and a reducing gas may be mixed and supplied into thechamber 1, or an Ar gas and a reducing gas may be supplied sequentially.

Next, the third aspect of the present invention will be described.According to the third aspect, a barrier metal film of TaN is subjectedto a treatment for etching the surface and forming nuclei of siliconatoms by use of a plasma of a silicon-containing gas (for example,silane, SiH₄, a hydride of silicon). Silicon, which is not a foreignmatter, has good adhesion to a metal, and the formation of nuclei ofsilicon atoms on the surface can increase adhesion between the metal ofa barrier metal film and a metal to be formed as a film thereon. By thismethod, a barrier metal film preventing diffusion of a metal andretaining adhesion to the metal is produced with good efficiency andwithout deterioration of performance.

As the silicon-containing gas, a disilane (Si₂H₆) gas or a trisilane(Si₃H₈) can be used in addition to the SiH₄ gas. If hydrogen cannot beused, an SiCl₄ gas, an SiH₂Cl₂ gas or an SiHCl₃ gas can be applied. Anysuch gas may be diluted with a diluent gas and supplied. By controllingthe dilution ratio or the flow rate of the gas, or controlling the powerof its plasma, it becomes possible to control the depth of etching onthe surface or the sizes of the nuclei of silicon atoms.

A concrete apparatus construction according to the third aspect of theinvention may be as follows: Using a barrier metal film productionapparatus, a source gas containing a halogen (e.g., achlorine-containing gas) is supplied to the interior of a chamberbetween a substrate and an etched member of Ta, and an atmosphere withinthe chamber is converted into a plasma to generate a chlorine gasplasma. The etched member is etched with the chlorine gas plasma to forma precursor comprising the Ta component contained in the etched memberand the chlorine gas. Also, a nitrogen-containing gas is excited, andTaN, a metal nitride, is formed upon reaction between the excitednitrogen and the precursor. The resulting TaN is formed as a film on thesubstrate kept at a low temperature to form a barrier metal film. Afterthe barrier metal film is produced in this manner, an SiH₄ gas plasma, agas containing silicon, is generated within the chamber to form crystalgrains of Si. That is, a barrier metal film production apparatus shown,for example, in FIG. 39 can be applied.

Alternatively, a concrete apparatus construction according to the thirdaspect of the invention may be as follows: A chlorine gas is suppliedinto the chamber, and an atmosphere within the chamber is converted intoa plasma to generate a chlorine gas plasma. An etched member made ofcopper (Cu) is etched with the chlorine gas plasma to form a precursorcomprising the Cu component contained in the etched member and chlorineinside the chamber. The temperature of the substrate is rendered lowerthan the temperature of the etched member to form a film of the Cucomponent of the precursor on the substrate. This process is performedusing a metal film forming device. The substrate having a barrier metalfilm of TaN formed thereon is housed in the chamber. Before the Cucomponent is formed as a film thereon, an SiH₄ gas plasma, a plasma of asilicon-containing gas, is generated within the chamber to form crystalgrains of Si. That is, the metal film production apparatus shown, forexample, in FIG. 29, 34, 37 or 38 can be applied.

An embodiment of the metal film production method and metal filmproduction apparatus according to the third aspect will be described,with the provision of the apparatus in the Cu-CVD 404 (see FIG. 28)being taken as an example.

FIG. 42 shows the conceptual construction of a metal film productionapparatus according to the twenty-first embodiment of the presentinvention. FIG. 43 shows the concept status of a barrier metal film inthe formation of nuclei of Si. The illustrated metal film productionapparatus has the conceptual construction of the metal film productionapparatus according to the fifteenth embodiment shown in FIG. 29, inwhich the gas supplied through the nozzles 21 is made different. Thus,the formation of the thin Cu film in the metal film production apparatusis the same, and its explanation is omitted hereinbelow.

As shown in FIG. 42, silicon-containing gas nozzles 228 are provided, assilicon-containing gas supply means, for supplying a silane gas (SiH₄gas), as a gas containing silicon, to the interior of a chamber 201above the surface of a substrate 203. An SiH₄ gas diluted with hydrogenis supplied through the silicon-containing gas nozzles 228, andelectromagnetic waves are shot from a plasma antenna 209 into thechamber 201, whereby the hydrogen-diluted SiH₄ gas is ionized togenerate an SiH₄ gas plasma (surface treatment plasma means). On thesurface of the substrate 203 admitted into the illustrated metal filmproduction apparatus, a barrier metal film 223 of TaN (see FIG. 31) hasbeen formed. Generation of the SiH₄ gas plasma results in the growth ofcrystal grains of Si and the appearance of H₂. While film formation isproceeding, crystal grains of Si are formed as nuclei on the superficiallayer of the substrate 203 by the etching action of H₂.

The formation of the nuclei of Si upon generation of the SiH₄ gas plasmais performed before formation of the thin Cu film 216 explained in thefifteenth embodiment of FIG. 29. That is, when the substrate 203 havingthe barrier metal film 223 of TaN (see FIG. 31) formed there on isadmitted onto the support platform 202, a hydrogen-diluted SiH₄ gas issupplied through the silicon-containing gas nozzles 228 prior to theformation of the thin Cu film 216 (see FIG. 29). Also, electromagneticwaves are shot from the plasma antenna 209 into the chamber 201 togenerate an SiH₄ gas plasma. The ratio of SiH₄ to hydrogen in thehydrogen-diluted SiH₄ gas is set, for example, as follows:SiH₄/hydrogen≦5/100. As the diluent gas, argon, helium, neon or otherdiluent gas can be applied in addition to hydrogen.

When the SiH₄ gas plasma is generated, the reaction

SiH₄→Si+H₂

proceeds. As a result, while film formation is proceeding, crystalgrains of Si are formed as nuclei on the superficial layer of thebarrier metal film 223 by the etching action of H₂, as shown in FIG. 43.The sizes of the nuclei of Si can be controlled appropriately bycontrolling the conditions for the plasma, the ratio of hydrogendilution, the flow rate of the gas, etc. The etching action of H₂removes the nitrogen atoms (N) of the barrier metal film 223, and canbring the state of the barrier metal film 223 having a two-layerstructure, a metal layer 223 a substantially composed of Ta (see FIG.33), and a TaN layer 223 b (see FIG. 33).

Since the SiH₄ gas is diluted with hydrogen, the crystallinity of Si canbe improved, and its nuclei are easy to form. Silicon, which is not aforeign matter, has good adhesion to Ta and Cu, and the formation ofnuclei of Si on the surface of the barrier metal film 223 can increaseadhesion between Ta of the barrier metal film 223 and Cu to be formed asa film thereon. By this method, a barrier metal film 223 preventingdiffusion of the metal and retaining adhesion to the metal is producedwith good efficiency and without deterioration of performance.

With the above-described metal film production apparatus, the SiH₄ gasplasma is generated within the chamber 201 accommodating the substrate203 having the barrier metal film 223 formed thereon, whereby crystalgrains of Si are formed as nuclei on the superficial layer of thebarrier metal film 223. Thus, adhesion to Ta and Cu can be improved.Consequently, the barrier metal film 223 can be formed with satisfactoryadhesion and anti-diffusion properties without becoming thick, so thatthe Cu wiring process can be stabilized.

The twenty-first embodiment described above can be applied to the metalfilm production apparatuses of the sixteenth to eighteenth embodimentsshown in FIGS. 34, 37 and 38. It is also applicable to the barrier metalfilm production apparatus of the nineteenth embodiment shown in FIG. 39.It is also possible to combine the flattening of the surface with Ar⁺upon generation of the Ar gas plasma in the fifteenth to nineteenthembodiments with the formation of crystal grains of Si as nuclei on thesuperficial layer of the barrier metal film 223. In this case, a commonnozzle can be used by diluting an SiH₄ gas with an Ar gas, and theflattening of the surface and the formation of Si nuclei can be easilyswitched by controlling the flow rate of the Ar gas.

While the present invention has been described by the foregoingembodiments, it is to be understood that the invention is not limitedthereby, but may be varied in many other ways. Such variations are notto be regarded as a departure from the spirit and scope of theinvention, and all such modifications as would be obvious to one skilledin the art are intended to be included within the scope of the appendedclaims.

1. A production method for a barrier film comprising: arranging ametallic etched member and a substrate within a chamber; forming aplasma of a source gas in the chamber so that the etched member isetched with the source gas plasma to form a precursor from a metalcomponent contained in the etched member and the source gas; exciting anitrogen-containing gas in an excitation chamber isolated from thechamber and supplying the excited nitrogen-containing gas into thechamber in which the source gas plasma is formed, through an opening inthe chamber; and terminating the supply of the excitednitrogen-containing gas to the chamber with retaining the source gasplasma in the chamber, thereby permitting a metal film to form on themetal nitride film.
 2. The production method of claim 1, wherein thetemperature of the substrate is controlled to be lower than that of thesource gas plasma during the formations of the metal nitride film andmetal film.
 3. The production method of claim 1, wherein the source gasplasma is generated by an electromagnetic wave from a coiled windingantenna disposed around the chamber.
 4. The production method of claim1, wherein the source gas is the source gas containing chlorine.
 5. Theproduction method of claim 1, wherein the nitrogen-containing gas is agas containing ammonia.
 6. The production method of claim 1, wherein theetched member is made of tantalum, tungsten, titanium or silicon whichis a halide-forming metal.